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Transition metals in organic synthesis: hydroformylation, reduction and oxidation
399
TRANSITION
METALS
IN ORGANIC
SYNTHESIS:
HYDROFORMYLATION,
REDUCTION
AND OXIDATION ANNUAL
SURVEY
LkSZLb
MARK6
Institute H-8200
COVERING
of Organic
Veszprem,
THE YEAR
1986x
Chemistry,
University
of Veszprem,
Hungary
CONTENTS
I.
Theoretical
II.
Hydroformylation
1.
Calculations
Hydrogenation
3.
Reactions
of CO to Hydrocarbons
Nitrogen-containing 2.
401
and Related
Organic
of CO
402
and to Oxygen-
or
Compounds
402 404
Hydroformylation a)
Co Catalysts
404
b)
Rh Catalysts
405
c)
Other
d)
Heterogeneous
Metals
e)
Modified
Systems
Coordination
5.
Water
408
Complexes)
410
(Homologation)
Carboxylic
4.
(Supported
Hydroformylations
Hydrocarbonylation Aldehydes,
401
as Catalysts
Acids
Chemistry
of Alcohols,
and Esters
Related
with
Ethers, 411
CO + H2
to CO Hydrogenation
and
Hydroformylation Gas
Shift
6.
Reduction
7.
Miscellaneous
with
III. Hydrogenation 1.
H Exchange,
2.
Hydrogenation
*
416
CO or CO + H20 Reductive
Tranformations
417 of CO and CO2
and Reduction D and T Labeling
419 420 420 421
of Olefins
Fe, Ru, and OS Catalysts
421
b)
Co, Rh, and Ir Catalysts
422
c)
Ni, Pd, and Pt Catalysts
424
a)
3.
414 Reaction
Asymmetric
Hydrogenation
of Olefins
No reprints available Previous reviewseeJournalof (Elsevier, 1987) 271.
References p. 5 I4
OrganomstallicChenistqLibrary 19
425
433
4.
Hydrogenation
of Dienes
and Alkynes
5.
Hydrogenation
of Arenes
and Heterocyclic
6.
Hydrogenation
of Carbonyl
-7
/.
Hydrogenation
of Nitro
8.
Miscellaneous
Hydrogenations
9.
Dehydrogenation
10.
11.
Hydrogen
338 438
443
Reactions
Hydrogenation
of C=C or C=C
b)
Hydrogenation
of C=O bonds
c)
Hydrogenolysis without
by Hydrogen Molecular
a)
Transition
Metal
b)
Low Valent
Transition
c)
Inorganic Metal
434
Compounds
a)
442
bonds
443 Transfer
444
Hydrogen
444
Hydrides Metal
Reductants
444 Complexes
in the Presence
444 of Transition
Complexes
d)
Reduction
e)
Organic
446
via Silylation Reductants
449
in the Presence
of Transition
Metals f)
Oxidation
1.
Catalytic Groups
2.
451
Electroreduction
IV.
Oxidation
of Hydrocarbons
or Hydrocarbon
02
454
a)
Oxidation
of Alkanes
b)
Oxidation
of Olefins
c)
Epoxidation
d)
Oxidation
with
353
and Photoreduction
454
with
Catalytic
454 454
or Alkynes
457
of Olefins
458
of Aromatics
Oxidation
of O-containing
Functional
Groups
02
461
a)
Oxidation
of Alcohols
b)
Oxidation
of Phenols
c)
Oxidation
of Aldehydes
d)
Miscellaneous
461 463 and Ketones
466
Oxidations
466
3.
Catalytic
Oxidation
of N-containing
4.
Catalytic
Oxidation
of P- or S-containing
Compounds
433
440
Transfer
Reduction
Compounds
Compounds
Organic
Compounds
461
Organic 471
401 5.
Catalytic
Oxidation
or Inorganic
6.
of Organic
Compounds
Organic 472
a)
General
b)
Oxidation
c)
Epoxidation
d)
Oxidation
of O-containing
Functional
e)
Oxidation
of N-containing
Organic
f)
Oxidation
of P- or S-containing
472 of Hydrocarbons
Oxidation
Transition
Oxidation
or Hydrocarbon
Groups
472
of Olefins
Stoichiometric High Valent a)
with
Oxidants
415
Organic
of Organic
Metal
of Hydrocarbons
Groups
485
Compounds
488
Compounds
Compounds
489
with
Complexes
491
or Hydrocarbon
b)
Epoxidation
c)
Oxidation
of O-containing
Functional
d)
Oxidation
of N-containing
Organic
e)
Oxidation
of P-, S- or Halogen-containing
Groups
491
of Olefins
496 Groups
498
Compounds
503 Organic 505
Compounds 7.
Electrooxidation
V.
Reviews
List Metal
507
and Photooxidation
508 511
of Abbreviations
512
Index
514
References
I. Theoretical
Calculations
Theoretical
calculations
showed
that the
1,2-hydride
shift
reaction: -
HMn(COjS
is considerably
more
(C0)4Mn-C(O)H
endothermic
than the
1,2-methyl
shift reac-
tion: CH3Mn(C0)5
This
explains
the apparent
CO [ll. Quantum tive addition
chemical
of pentane
[2]. An extended reactions systems
Refcrcnces p.
considered
(Co),Mn-C(O)CH,
inability
calculations onto
species, a mechanism
of hydride
to migrate
were performed
HPt(PPh3)X
Hiickel MO analysis
by do MLn
5 I4
-
toward
on the oxida-
(X = Cl,Br,I)
complexes
of H-H and C-H activation
such as Cp2LuR involving
was reported.
a transition
For the
state with
402
an electron-deficient
coordination
[31. A semiempirical to ethene
study
was performed,
VB analysis
-
which
dials
has been
[51.
II.
Hydroformylation Hydrogenation
cates.
The Co(I)
trifluoroacetate
nium(III) styrene
significant ions were through
these Ru(II1) observed backbone. various
Carbon
were
amounts
in 0~0~ to vicinal
orbital
point
of
of CO
was
either
incorporated
or Nitro-
CpCo(COD) were
formed
rings
sili-
161. Ruthe-
linear
poly-
and the reactions studied.
and hydrogen
Co(I)
in situ from -was used. At low
into sulfonated process
with
on alumina
prepared
CO and H2 were
hydrocarbons
studied
or supported
0 2 and the benzene
aliphatic
liqands
and to Oxygen-
of olefins
an ion-exchange
monoxide
by
Compounds
or the complex
ions with
between
Reactions
in solution
catalysts
augmented
of olefins
from the frontier
of CO to hydrocarbons
at 200-250°C
from 0x0 porphyrins
/4!. The concerted
in the oxidation
Organic
Co(I1)
pressures
functions
of CO to Hydrocarbons
Hydrogenation
found to be reasonable
to the oxygen
and Related
gen-containing
catalysts
wave
analyzed
view
1.
step
was
transfer
on EHT calculations
of an olefin
is the Eirst
-
based
of the resultant
[3+21 cycloaddition
mode
of oxygen
of
H/D Exchange
was
of the polystyrene
reacted
to give
at 150'
and oxygen-containing
compounds
171. Benzene
solutions
CO catalytically
produce
with
300 nm light.
tion
between
rium)
The
[Rh(OEP)12
and HCORh(DEP)
of ethylene
gas in the presence
qlycol
of Ru carbonyl
by ammonium,
phosphonium,
activity
for ethylene
glycol
cant effect; the best anol) also
solvents
results
ability with
[9]. The
in N-methylpyrrolidone by the addition
catalysts
formation
as solvent
of a large
excess
bond
[8l.
500 bar)
halides.
was observed
was markedly
(Ph3P)2NC1.
a siqnifi-
12 and 15 gave
glycol
of imidazole
is
Highest
with
had also
between
of ethylene
equilib-
from synthesis
(240°C,
and iminium
numbers
irradiated
by the reac-
of the Rh,C
of the solvent
acceptor
when
in a thermal
and ethanol
formation
of H2 and
occurs
(formed
cleavage
promoted
The electron-accepting
and methanol
of CH20 probably
by the homolytic
formation
in the presence
formaldehyde
Formation
HRh(DEP)
initiated
of
(and meth-
increased compounds,
403 especially
benzimidazole
an ammonium anionic
Ru species
genated
products
systems
in AcOH
the activity stability
[lo]. Probably
ion and acts
as the cation
[ll]. Conversion
was
studied
as solvent.
of pressure
Different oxygenates
proposals
increasing
The reaction
(220-240°C,
mixture glycol
[18]. Rhodium excess
in addition
ethylene with
glycol
catalyzed
References
p. 5 I4
ligands.
by
2000 h-l with
70% selectiv-
[16]. In the hydrogenation complexes
[17,18]
were
while
formation and hence
and the sta-
dependent
Best results
led to the
significant
were
catalytic
on the
obtained
arylphosphines
of the phosphidoinhibited
as solvents
from synthesis
cataly-
of tertiary
by Ir carbonyl
]lP]. By monitoring
gas at 200°C of [Rh(CO)4]-
ammonium
however,
cation
in the hydrogena-
1,2-Dimethyl-2-imidazolidti
it was observed
anion was,
donor
activity
(at 80°C).
used
concentration
as a proton
The effect
accelerated
complexes
if a tertiary
bly acted
of ethylene
+ N-methyl-2-pyrroli-
of the reaction
[Rh9P(CO)21]2-
The tetracarbonylrhodate active
Rh were pres-
by Rh-phosphine
like PPri
and conductivities
increasing
of C2
found to be strongly
to alcohols
or tetraglyme
red spectra
of the formation
formed -in situ from Rh(C0)2(acac) and of tri-n-alkylphosphines (lo-40 moles/mole Rh)
tion of aldehydes none
were
anion
pres[13].
The synthesis
was about
catalyzed
of phosphites
cluster
cases
H2 partial pressure
a Rh4(C0)12
was colorless
alkylphosphines
and all types
In both
with
Co
At 300°C and 2000 bar the turnover
of the phosphine
carbonyl
studied.
of CO partial
500 bar) the selectivity
bulky
a large
to
its
of CO + H2 with
be significantly
glycol
of the catalyst
structure
showed
could
for ethylene
was
[14,15].
gas using
as catalyst
of CO to ethylene
sis
catalyst
contributed
enhanced
gas over oxide-supported
the temperature.
frequency
with
metal
mainly
increased
for the mechanism
papers
from synthesis
system
glycol glycol
independent
from synthesis
in two polemic
bility
1O:l Ru:Rh mixed
on the conversion
to ethylene
sure but was practically
ity.
to
active
gas into C2 oxy-
and the Ru component
to ethylene
the selectivity
done
is converted
1121.
and Rh catalysts
glycol
of synthesis
The Rh component
of the catalyst
The effect
ented
with
the amine
of the catalytically
that
infra-
the yield
and 200 bar
increased
in the reaction catalytically
was also present:
of
mixture. only
this proba-
[20]. phosphines
catalysts
on the hydrogenation
(250-270°C,
650-750
of CO
bar) has
404 been
Triarylphosphines
investigated.
activity
and
selectivity
trialkylphosphines
found
to have
The clusters were
used
composed
LPtRh5(C0)15]-,
The results cluster
with
those
and Pt(acac)2.
product
and was
glycol
i211. 2-
IPtRh4(CO)121
at 230°C and obtained
with
Ethylene
but Pt increased
that Pt acts
whereas The complex
mixture
and
the
1400-2000 catalysts
glycol
MeOH
was
in
formation.
in the form of a mixed
Pt-Rh
[221.
Both catalyst
Ru02.xH20
and RUDER
precursors
formaldehyde
and Me3N
is the primary
reaction
participates
ly leads
to ammonium
carbonyls
See also
have
for the conversion
to N-methylformamides
osmium
formation,
for ethylene
[Rh5(C0)15]-,
compared
favored
suggest
activity
enhanced
formation.
for CO hydrogenation
were
of Rh(acac)(C0)2 the
glycol
methanol
from the reaction
catalytic
as catalysts
cases
promoted
isolated
a high
bar. The results
most
for ethylene
mostly was
IrZ(C016(PPh3)2
such as PPh3
showed
to be effective
340 bar.
product.
in a water-gas
also
found
of CO + H2 + NH3 mixtures
at 230°C and
reaction
carbamate
been
shift
Probably formed
reaction
as byproduct. some catalytic
Water
in the
and subsequent-
Rhodium, activity
iridium
and
[23,24].
12011.
2. Hydroformylation a) Co Catalysts
Capillary
GC and GC-MS
ed by hydroformylation alcohols
that
formylation decreased amines
could
be formed
of propene by py,
increased
on the rate was
found
were
present
and BuNH2;
The
of HCo(CO)d formation
than
acid was
showed
suitable
Co dodecanoate simpler
mixture
that
obtain-
all 24
[251. The rate of hydroas catalyst
the inhibiting
order.
to be a more
of propene
of the alcohol
n-alkenes
Co 2-ethylhexanoate
in the stated
hexanoate formylation
using
(iBu)3N
was noted
of 2-ethylhexanoic
analysis
of Clo_13
effect
same effect
because
of these
of the amines
[261. Cobalt catalyst
was
2-ethyl-
for the hydrothe regeneration
than that of dodecanoic
acid
[27]. Hydroxycitronellol -l-heptene catalyst
was prepared
by hydroformylation
from 2,6-dimethyl-6-hydroxy-
in the presence
of a Co/phosphine
[28j. The use of Bu2P(CH2)2SiMe(OMe)(CH2)2PBu2
as ligand
405 in the hydroformylation resulted
of propene
in 97% selectivity
for straight-chain
The aminophosphine-containing
Co carbonyl and
[Co(CO)3(Ph2PCH2CH2Ne3)21(PFs)2 were The
tested ionic
as catalysts
complex
two-phase
system
but
[301. The chiral prepared
could
optical
See also
b)
was
[291.
of l-hexene.
in an aqueous-organic catalysts
solvent
was rather
(1, L = (RI-(+)-PMePh(o-anisyl))has
as catalyst
for the hydroformylation
L was observed
induction
products
[Co(CO)3(Ph2PCH2CH2NMe2)12
of both
at 89'C and 80 bar CO + H2. Under of the ligand
catalyst
complexes
for the hydroformylation be used also
the activity
cluster
and used
with Co carbonyl
such conditions
and cluster
reported
been
of styrene
decoordination
(2) was obtained.
No
CO and H2 in the presence
of
[31].
[43,451.
Rh Catalysts The reaction
Rh4(CO)12
cyclopentenones tuted
of enynes
as catalyst
with
at 100°C and 200 bar gave
and unsaturated
lactones
[321
formyl
dienes,
(R=Ph or p-substi-
Ph):
R _,IR-
-R
+
Ra
References p. 5 14
I R 0
RYR
+
low
gR ‘
Chemical propene ment
oscillation
with
a Rh-phosphine
for oscillation
of butyraldehyde formylation
Using
formylation followed
by hydrogenation
of 1-hexene
31P NMR.
with
The CO-free
yield
complex
to the monocarbonyl
tion mixture
[361. Hydroformylation
l-11 bar and 40°C with high n/i
caused
ratios
a systematic
reaction
mixture
drop
of this ratio.
[Rh2( lJ-L)2(COD)212'
and
Addition catalytic 5 bar.
of tBuSH
activity
complex
allylbenzenes
by independent
were
[Rh( /.t-SBut)(CO)Lj2
High
yields
pressure using
of linear
catalytic
(L = PPh3, aldehydes
including
using
of the
was the active Rh complexes
(L = 3) were
1381.
increased
of 1-hexene
its
at 80°C and
of the dinuclear probably
[39]. Several
substituted
the dinuclear
Rh complex-
P(OPh13)
obtained
at 80°C
of 1-hexene
and stoichiometric
Cp2Zr(CH2PPh2)2.
prepared
of l-hexene
slightly
P(OMe)3,
were
hydroformylation
[Rh(b -SBU~)(CO)~]~
diphosphines
pathways
at
increase
The two Rh complexes
hydroformylated
could
as catalyst.
IR examination
the formation
[Rh( K-SBut)(CO)(PPh3)12.
act as catalysts
es
for hydroformylation showed
which
CO to the reac-
ring binuclear
to HRh(CO)(PPh3)3
using
was examined
for the hydroformylation
IR and NMR spectra
studied
-+ P(OPh)3
!Rh2(I_I-L)2(CO)4]2c
gave
hydroformyla-
formed
that HRh(CO)!P(OPh)3]3
1371. The large
as catalysts
cleavage
at 1 bar: pressure
form of the catalyst
and used
was
of l-hexene
obtained
suggested
has been
of
catalyst
and ether
by admitting
Rh(acac)[P(OPh)312
were
catalyst
!341. Hydro-
a Rh carbonyl-PPh3
HRhlP(OPh)3]4
back
amount
the formation
be diminished
HRh(CO)[ (P(OPh)3]3
require-
133!. Hydro-
of
[35]. Stoichiometric
be converted
Very
as promoters
of
is accompanied
deterioration
could
with
mixture
catalysts
of the aldehydes
in 75% overall
important
of a certain
reaction
Rh-PPh3
phosphines
compounds
of CH2=CHCH20But
HO(CHZ)40H tion
with
and a rapid
bidentate
and phosphonium
The most
was the presence
in the liquid
alcohol
side reactions
activity. Ph3PO
trimer
in the hydroformylation
catalyst.
to occur
of ally1
by several
was observed
as catalysts. i401. LOW
was performed
amounts
The latter
of various
ligand
furnished
407 the most
active
catalyst
Nitrogen-containing
system
[41].
cyclic
olefins
(N-substituted
nes and N-methyl-1,2,3,6_tetrahydropyridine)
were
nortropidi-
hydroformylated
with
Rh + PR catalysts prepared in situ. Regio- and chemoselectiv3 ity of the reaction was practically independent of the phosphine in the case of nortropidines;
dine
the selectivities
by the presence See also
c)
Metals
catalyst
production
ligand
and
[421.
UV irradiation
at ambient
catalytic
solvents
for these
Co2(CO)9
temperature
the bimealcohol
ranged
between
effect against
The platinum
might
catalysts.
be explained
complex
and heptane
system
(4, Y=H) was
were
(4,Y = EtCO)
formed
an in-
of olefins, were
the best
It was proposed
that the
reactivity
of
[45].
to give products Along
with
in comparable
the alkyl could
conditions
showed
found to catalyze
and heptene-2
as substrate,
under
Hydrogenation
these
Alcohols
by the high
acyl complexes
(90 and 60%, respectively).
was used
under
alone.
by the
and RUDER
for the hydroformylation
cobalt
of heptene-1
is catalyzed
and pressure.
bimetallic
or RUDER
mixed-metal
[HRu(CO)~I-
and propene Ru(C0)4(PPh3)
+ Ru~(CO)~~
synergistic
(4,Y = Et) and
with
Linear
ratio
was also observed
activity
with
C8 alcohols
of ethene
and olefins
compared
linearity
if the Cr/Co
Ru(CO)~(PP~~)~,
[44]. The Co2(CO)S
formylation
investigated
[43].
complexes
of aldehydes
was
+ HCO(CO)~(PBU~).
efficient
Hydroformylation
ethene
by the phosphine
such as Et3N
of 1-hexene
Cr(C0)5(PBu3)
was most
5O:l and 1OO:l
creased
influenced
bases
tetrahydropyri-
as Catalysts
Hydroformylation
Ru(0)
the less basic
[106].
Other
tallic
were
of added
with
the hydroof high
CS aldehydes amounts.
also
If
and acyl complexes
be isolated.
Catalysts
formed
in situ from Pt(COD)2, Ph2POH and a tertiary phosphine were also -active and in the absence of a tertiary phosphine ethene produced mainly
3-pentanone
Referencesp.514
under
hydroformylation
conditions
1461.
Ph2 p\ pt,PPh3
.o H; O-P’
Y ‘ Ph2
See also
d)
11871.
Heterogeneous
Systems
The supported used
as catalyst
and 20-60 during
bar.
(Supported
tetranuclear
Complexes)
Co-P cluster
for the hydroformylation
The activity
repeated
of olefins
of the catalyst
use (up to 10 times)
(5) was prepared
and
at llO-15O'C
did not decrease
[47].
(CO)2 ,Qo,2 SIL
/ u-
’
P
-
-‘ cco,2co~c
/
5 co (CO)2
0
Phosphine-bearing carriers
for cobalt
transformed which
under
behaved
Formation products
polyphosphazenes
hydroformylation
the reaction
conditions
like the homogeneous
of HPR2,
benzene,
was observed
(6) and
catalysts.
benzyl
into
analogues alcohol
(7) were Both
soluble
COAX and other
used
systems
complexes + XPR2.
deqradation
[48].
PhO
PhO
/ \ ,0 -cl- P N# N ‘ fl ,OPh 1
PhO,
PhO, PPh2 6
PhO/PNN/P\OPh 7
as were
PPh2
409
Hydroformylation catalyst
systems
clusters
bonded
tertiary
amine
obtained
The industrial
lary
PPh3
and
forces,
lysts based Polymeric
tested
containing ring was
aldehyde
formation
has
stable
available
group
the unsaturated
showed
good
selectivities
The activity tion was found dependence
solvents.
of Rh-zeolite
to depend
upon
the partial
to that
reported
Rhodium
zeolite
A catalysts
by ion exchange
liquid
phase.
similar
but
more
rapidly
containing
in the liquid [56 1.
by a RhNaY
proceeded
zeolite
to heterogenize
References
p. 5 I4
Pt catalysts
were
catalyst
onto poly-
[547.
for hydroformyla-
surface
The rate were [551.
Rh prepared
as catalyst
phase
catalyst
were
reaction
for
and in the
IR studies
polymeric
pre-
in THF
formation
applied
transform
of
cata-
of the two catalysts
in a homogeneous-like
for
E-styryl-
phosphine
the ion-exchanged
Polystyrene-divinylbenzene-based used
either
activity
phase
with
of preparation.
in the vapor
In situ Fourier
resins
hydroformylation
Rh were
of hexene-1
for
of CO, H2 and propene
for homogeneous
The vapor-phase
hydroformylation reaction
pressures
for
studied
prepared
X and Y catalysts
or intrazeolitic
the hydroformylation
aldehyde
on their method
similar
was
The supports
The supports
for normal
on the
hydroformylation
pared
grafting
used
[51]. The
and selective
Rh(C0)2(acac)
copolimers.
in different
(Et2N)2PC1.
and the hydrogenation
of Rh(1)
by reacting
an amino
were
functionalized
diphenylphosphine-polyropylene by y -radiation
with
ligands
lifetime
amine
Cata-
as substituent
active
in
capil-
of propene.
of diisobutylene
of dicyclopentadiene 1531. A series
dissolved
by strong
copolymer
to be the most
been prepared
propylene
hydrogenation
by reacting
and these
[52]. The catalyst
formed
life
for 1500 h 1501.
prepared
the -CH2NHCH2CH20H
commercially
the aldehyde
support
were
were
[Rh(C0)2C1]2
found
the hydroformylation
lysts
supports
for the hydroformylation
catalyst
Rh-loaded,
of HRh(CO)(PPh3)3
on a porous
ligands
from
aromatic
available
of catalyst
step but later aldehyde
divinylbenzene-styrene
prepared
as catalysts
or commercially
for the hydroformylation
on CL -alumina
group-containing
using
(n = 0,1,2,4)
first hours
applicability
immobilized
was
studied
[491.
aminophosphine
Complexes
the
was the slow
rate determining
liquid
amines
During
resins.
was
from RhnCo4_n(CO)12
to tertiary
hydroformylation became
of dicyclopentadiene
lost Rh
of propene
reported. pathway
phosphines
for hydroformylation
was
of
The [57]. were U -olefins
410
in the presence
of SnC12.
The catalysts
(95%) to linear
aldehydes
[58]. Copolymerization
(8)
with
which
styrene
was
catalyzed
with
PtC12
JO-75%
was of
selectivity
of the phosphine
The resulting
and SnC12.
the hydroformylation
aldehyde
high
gave a phosphinated
and divinylbenzene
loaded
displayed
of styrene.
enantiomeric
purity
polymer
chiral
The resulting
complex
hydrotrop-
[ 59 ij .
8 PPh2 The chiral styrene
ligand
was used
catalyst
(9) attached
for asymmetric
to linear
or cross-linked
hydroformylation
O-JO%
in the case
Optical
yields
vinyl
acetate
or N-vinylphthalimide
as olefins.
several
loss of enantio-
catalysts
could
selectivity
be reused
but their
catalystic
times
between
poly-
Pt + SnC12
systems.
of styrene,
ranged
with
without
activity
gradually
The
decreased
!601.
--_ n Q-&j-J 9
H
-
P
/
p \
\/
-
e)
Modified
Ph2PR,
hydroformylation Selectivity See also
-
Hydroformylations
Polynuclear (Ph2PH,
\/
Co carbonyl Ph3P,
Bu3P,
and consecutive
of pentadecanol
[105].
complexes
dppe)
were
containing used
hydrogenation
formation
was
phosphine
as catalysts
ligands
for the
of I-tetradecene.
31-348
1611.
411
3. Hydrocarbonylation
(Homologation) of Alcohols, Ethers, Alde-
hydes, Carboxylic Acids and Esters with CO + H2 The catalytic activity of [Ru(CO)313]- in homologation of MeOH, Me20, MeOAc, formates, and alkyl orthoformates was discussed [62]. The selectivity of acetaldehyde formation in the hydrocarbonylation of methanol with Co12 as catalyst (150°C, 200 bar CO + H2) could be improved by adding diphosphines Ph2P(CH2),PPh2 (n = l-6) to the catalyst system. The main species present under the reaction conditions was [Co(CO)xPyliCo(CO)4] (x + y = 5; P = a phosphine moiety) [63]. The influence of several furfurylphosphines and their phosphonium salts, and of furylphosphines on the homologation of methanol to ethanol was investigated using Co as catalyst metal and I2 as promotor. The best results with respect to selectivity and conversion were obtained with the bidentate ligands (10) and (11) [641.
Ph2P g
Homologation of MeOH to EtOH using the Co12 + Ru12(C0)2(PPh3)2 + NaI catalyst system was found to be second order in MeOH. The complex [MePh3P][Ru13(CO) 3 ] was isolated from the reaction mixture and proved to be an active homologation catalyst also in the absence of cobalt [65]. The influence of (12) and (13) on the homologation of MeOH to EtOH was investigated using Co(OAc)2.4H20 + RuC13. 3H20 (2O:l) as catalyst and I2 as promoter. The potentially bidentate phosphine (12) gave a much more active catalyst system than the potentially tridentate phosphine (13) [661.
12
13
The ligand (14) was tested in the homologation of MeOH with Co + Ru catalyst and MeI promotor. Under optimum conditions selec-
References
p. 5 14
412
tivity large
of EtOH amounts
formation of Et20
about
was
were
60% but at high
formed
conversions
1671.
14 CH2PPh2
Bifunctional noble
catalysts
i68]. Homologation
MeOH
100 bar) Neither
was
achieved
synergistic
effect
Co2(COj8
adding
low reaction
with
a small
temperature
Hydrocarbonylation
um complexes aldehyde were
crotonization
(12OO)
L711.
these
products
diethyl
qlycol
Co + Rh mixed-metal
tigated
was
at llO°C
obtained found
later
of co2+ which
in a relatively
substituted of qlycol
aldehyde
Rh(CO)(PPh3)2C1 and the reaction -chain
bromide
took place.
state
as
at a rather
at 170-180°C
with
studied. COAX
Heavy
and
Rhodiacet-
byproducts and of
to ethylene
systems
has been
C2 selectivities
first
maintains
a
i72]. Hydroformylation
inves-
(= 65%)
catalysts.Glycolaldehyde few hours
of the reaction:
to methanol This
effect
the rhodium
and of glycolmay
be due to
catalyst
for some
[73]. The use of pyridine
greatly
in the hydroformylation
was
carbohydrates
Highest
as solvents
as catalyst.
benzyl
and its hydrogenation
in the
oxidized
pyridines
to 2-phenyletha-
of aldolization
catalytic
I
to be
using
product.
of formaldehyde
glycol
found
has been
+ Rh4(C0)12
only
hydrogenation
to ethylene
the presence time
CoC12.6H20
to be formed
only
aldehyde
and 100 bar.
with
1691. In
(84-87%)
propane
mainly
of acetaldehyde
to qlycolaldehyde
were
of 6:l
and working
ether:
was the main consisted
formaldehyde using
system,
of water
mainly
acetal
formed,
catalyst
amount
system.
significant
of Co, Ru and
alcohol
selectivity
Rh and Co complexes
furnished
dimethyl
also
of benzyl
of 2,2-dimethoxy
120 bar CO + H2 using
ratio
in the presence
of
CO + H2 !200°C,
catalyst
the most
at a Ru:Rh
high
mixed-metal
+ RuC13
with
and 450 bar, Co and Ru were
be performed
promoter,
to ethanol
active,
to PrOH
1701. Homoloqation
synergistic no1 could
were
was observed
CO + 2H2 at 200°C
I and a heterogeneous
for the homologation
a Ru + Rh mixed-metal
alone
of EtOH
of Co,
tested
of methanol with
of the metals
the homologation with
composed
(Ru, Rh or Re) were
metal
enhanced
the
of formaldehyde
Parafonnaldehyde
was used
or
formation with
as substrate
run at 70°C and 50 bar CO + H2 [74]. Straightsuch as trioses,
tetroses,
pentoses,
and
413 hexoses were obtained in good yields by reacting formaldehyde with CO + H2 in the presence of Rh(CO)(PPh3)2Cl and Et3N at 120°C and 120 bar. Carbohydrate formation under such conditions was due mainly to an amine-catalyzed condensation of glycol aldehyde formad by the Rh-catalyzed hydroformylation of formaldehyde [75]. The ruthenium-catalyzed homologation of acetic acid to propionic acid with synthesis gas was shown to proceed through the following consecutive reactions: hydrogenation of acetic acid to ethanol (and esterification to ethyl acetate) and carbonylation of the alcohol to propionic acid. Alkyl iodides were also found in the reaction mixtures and probably played a role in the carbonylation process [76]. Reaction of methyl acetate and synthesis gas at 170°C and 330 bar with a catalyst charged as Co12 + LiI + NPh3 (molar ratio 2.5:1.5:1) resulted in the formation of acetaldehyde and acetic acid according to the following stoichiometry: MeCOOMe + H2 + CO. -
MeCHO + MeCOOH
Acetaldehyde was obtained in 98% yield: minor amounts of methane and ethyl acetate were the only byproducts [771. Homologation of methyl acetate with CO + H2 using rhodium chloride/methyl iodide based catalyst systems under mild conditions (150-160°C, 40-60 bar) was reported. The activity of the catalyst was significantly increased by the addition of phosphine oxides. Predominant reaction under such conditions was the formation of propionic acid:
CH3COOCH3 + 2C0 + 2H2
-
CH3CH2COOH + CH3COOH
In combination with Ru mainly the alcohol moiety was transformed into its next homologue [781: 2CH3COOCH3 + 2C0 + 2H2
-
CH3COOC2H5 + 2CH3COOH
The effect of Lewis acids on the homologation of methyl acetate to ethyl acetate with ruthenium carbonyl iodide catalysts was investigated. Al and Sb derivatives favored the carbonylation steps of the reaction resulting in high (72%) selectivities to acetic acid; Ti derivatives favored carbonylation + hydrogenation increasing ethyl acetate selectivity up to 70% [79]. The homologaReferences
p. 5 14
414 tia
of methyl
-promoted pathway
esters
ruthenium
of the reaction
moter
employed:
ethyl
esters
process
with
the alkoxy
moiety
found
to be the most
catalyst
effective
were
catalysts
the alcohol
be transformed
found
tigated gous
and
180°C,
lactone
Rh catalysts
furnished
4. Coordination
for the
in the presence
Related
of
in the case of with
iodide
was
Rh-based
to the usual
Ru-based
with
CO + H2. could
[82].
catalyzed
by Rh and Co complex-
and 200 bar has been Formation
only with Co catalysts
only mono-
of
Homoloqation
of esters
of I2 as promoter.
Chemistry
tested
important
acid part of the ester
homologue
respectively,
was observed
were
[Sl]. Ruthenium-assisted,
of lactones
in the presence
of
iodide
to be superior
its higher
the formation
(especially
of ionic
and the carboxylic
into
pro-
(2H2 + CO).
for the homologation
Hydrocarbonylation es at 230°C
by Ru
of the iodine
was the most
esters
and 420 bar
of iodine-
The predominant
was
Co + Ru catalysts
and a combination
systems
or Co-based
reaction
acyl reduction
was promoted
esters),
in the presence examined.
on the nature
of carboxylic
at 200°C
ethyl
Both
with Me1
carbonylation
gas
has been
LiI the main
whereas
promoters
synthesis
depended
[80]. Homogeneous
reductive iodine
with
catalysts
(14-48%
and dicarboxylic
acids
to CO Hydrogenation
inves-
of the homoloyield), !83].
and
Hydroformylation
Based it was
on model
suggested
of CO occurs
via
to coordinated on the next
studies
that
with
successive
[84]:
cycle
complexes
catalyzed
intermolecular
CO. A catalytic
page
isolable
the homogeneously
based
of Ru and OS hydrogenation
additions on these
of H- and H steps
+
is shown
415
M
-
H2
M’CHb
H* + MH
M’CO CH30 ‘H
H+ + co
A quantitative relationship was found between the effect of bases on the deprotonation of HCo(C0)4 and their inhibiting effect on the hydroformylation reaction [851. The acylcobalt tetracarbonyls nPrCOCo(C0)4 and iPrCOCo(CO)4 react with H2 or HCo(C0)4 to yield nPrCH0 and iPrCH0, respectively. These reactions are part of the catalytic cycle in the industrially important hydroformylation of propene. The kinetic results support the conclusion that under the conditions of catalytic hydroformylation
( >lOO°C
and > 100 bar
CO + H2) the reaction with H2 is mainly responsible for aldehyde formation [86]. The reaction of HCo(C0)4 with ethyl acrylate under CO results under kinetically controlled conditions (c 10°C) in the branched-chain alkyl Co carbonyl complex; under thermodynamical control (> 25OC)the alkyl complex is transformed into the straight-chain acyl Co carbonyl. This effect agrees with the known influence of temperature on the distribution of isomeric aldehydes in the catalytic hydroformylation of ethyl acrylate [871. Triarylphosphines undergo P-C bond scission under hydroformylation conditions (190°C, 140 bar CO + Hz) in the presence of co2(co)8 to give a variety of hydrogenolysis and CO insertion products. Aryl group Er&lhg
is also observed when PR3 and PR;
are subjected to the above conditions.
In
the presence of an olefin
the phosphorous-aryl bond cleavage proceeds at a much slower rate [88]. Formation of clusters was found to be the cause for deactivation of rhodium carbonyl catalysts used in hydroformylation.
References p. 5 14
416 Oxygen
strongly
steps,
the relatively
could
undergo
vation
promoted
The mechanism studied
complexes ed that acid,
SnC12
-halogen
dride a very
The
synergetic
tive than
the
of activity
amines
catalyst
active
highly
long
with
Fe/Ir
the catalytic
systems,
choice
investigated step
catalytic
About
This
mixed ac-
for the
and secondary
react
do not give which
which
after
a
is a very tempera-
solvents;
it
a relatively
[Ru(bpy)2(CO)H]PF6 leads
active
i941. Reaction
at room
or nonpolar
with CO2
furnished
complex
has
to H2 formation)
is probably
reaction
The
more
of Ru3(C0)12
blue
(which
metals
[931.
CO2
reaction
shift
VIII
50% increase
towards
i95]. The complex
at
the i921.
of magnitude
amines
only
hy-
showed
studied.
inert
activity
and its protonation
in the water-gas
of Group
that primary
in polar
elim-
reaction that
has been
gas shift reaction
is insoluble
kinetically.
zeolite
indicated
was pyridine
a dark
for the water
period
Na-Y
but the amines
aliphatic
and was
its highest
activity
It was shown,
bpy yields
the reductive
alone.
systems
in a a tungsten-
in the case of Fe/Ru
carbonyls
catalyst
induction
[90].
i9ll. The cluster
carbonyls
two orders
The best
been prepared
mining
metal
active
with
was rate-determining
reaction
found
active
catalyst
to Pt
by HFe(CO;
involves
studies
metal
about
Tertiary
The catalyst
reaches
was
reaction.
with
conclud-
as a Lewis
for the water-gas-shift
systems.
of Ru3(CO)l2
of the
It was
bonded
on hydrated
gas shift
were
individual
to form carbamates.
moderately
reactions
CO if irradiated
adsorbed
of mixed
water
increase
yield
complexes
as a co-catalyst:
intermediate
activity
which
gas shift
ture.
mechanism
was observed
Amines water
suggested
synergism
carbonyls
by Pt-Sn
cycle.
is catalyzed
under
effect
pronounced
metal
reaction
~20 and the cluster
in the homogeneous most
ways
and spectroscopic
between
reacti-
stoichiometric
and water
[HFe3(CO)11]-
Kinetic
reaction The
gas shift
high catalytic
60-18OOC.
in partial
catalyzed
and as a ligand
of SnCl<,
of H 2 from a dinuclear
anion
resulted
in
still
reaction
of DMF
lamp.
ination
occured
in the beginning
in the cataiytic
act in several
gas shift
Clustering
[89].
involved
may
The water
which
by investigating
as the source
9:l mixture
formed
of hydroformylation
possibly
5. Water
formation.
clusters
declusterification
of the catalyst
has been
cluster
small
catalyzed
the rate-deterby
417 [Ru(bpy),(CO)C11+ [961. The water-gas shift reaction catalyzed by bis(bpy)-carbonyl-Ru(I1) complexes has been investigated. All the species involved in the catalytic cycle (which is shown below) have been isolated or characterized by spectroscopic methods [971.
H30+T
[Ru (bpy)g W~~O:12~H20
[Ru (bpy)K0)2]**
[Ru(bpy)2KO)Hf
OH[Ru (bpy)2KO)KOOHf
For a correction of AS 1985 ref. 66 see [98]. See also [23,105].
6. Reduction with CO or CO + H2g Reduction of ketones to secondary alcohols was achieved with 4 -Ph4C4CO)(C0)3Ru as catalyst
CO +-H20 at 105OC and 30 bar using ( 3
in THF solution. The reaction was accelerated by addition of Na2C03 [991.
The Al symmetry
vCo vibrations of the carbonyl complexes
(L = substituted derivatives of phen), were determined. MOM A correlation was found between these values and the catalytic activity of the systems composed of RUDER
or Rh6(CO)16 and the
corresponding phen derivatives in the hydrogenation of nitrobenzene with CO + H20
[loo]. The reduction of nitrobenzenes to the corre-
sponding anilines was achieved with a series of Ru and OS phosphine complexes using H2, H2 + CO or CO + H20 at 120°C and 70 bar in 2-ethoxy-ethanol as solvent. Addition of KOH increased the turnover numbers. The reaction was best carried out under water gas shift conditions [loll. Reduction of g-nitrostyrenes
(15) to indole
derivatives (16) by CO is catalyzed by Fe(CO)5, Ru3(CO)12, and Rh6(CO)l6 at 220°C and 80 bar in toluene solution. In small amounts also amines (17) are formed by hydrogen abstraction [102].
References p. 5 14
418
Hydrogenation
of
CI,p -unsaturated
CO + H20 and Rh4(C0)12 amine moieties selectively. effective readily
was
catalyst
studied.
than
supported
the homogeneous
one
to aniline
was
less active
compounds
on polymers bonds
catalysts
were
hydrogenated
generally
more
(18) were
in good yields
under mild
as catalyst
with
containing
were
[1031. Azidoarenes
derivatives
CO + H20 and RhC13. 3H20 catalyst PdC12
carbonyl
The C,C double
The resin-supported
transformed
15OOC).
17
16
15
conditions
with
(20 bar,
[104].
co + w
N3
18 Reduction olefins
with
of various
CO + H20 using
ied. The activity depended
on the
structure
amine
containing gas
tives
for the reduction
shift
urated
aldehydes
diamine
systems
droformylation
shift
with
the
showed
gave
of aldehydes. hydrogenated
high yields
and reduction
catalysts
component. catalytic diamines
activity
100 bar)
The role
2-arylacrylonitrile
d,(3-unsat-
from olefins
N-alkylvia hy-
can be trans-
under
in the presence
of the Rh catalyst
formed
for the
aldehydes;
2-arylpropionitriles
water
is to hydroge-
in the base-catalyzed
CH20 N-Me - morpholine
-
Ar-C-CN
gas
of RhC13.3H20
reaction
[1061:
Ar -CH2-CN
di-
the best addi-
With pyridines,
to saturated of alcohols
strongly
The ethylene
were
of
was stud-
systems
[1051. Arylacetonitriles
into
(200°C and
precursor.
+ amine
high
N-alkylated
formaldehyde
conditions
as catalyst nate
catalyst
and carbonylation
of the catalyst
of the amine
reaction;
were
groups
Rh6(C0)16
and selectivity
water
formed
functional
Rh -Ar-CH-CN CO+H20 kH3
419
Nitrobenzene derivatives p-RC6H4N02 (R = Me, Cl) were reduced to the corresponding anilines with CO in aniline solution in the presence of NiX2L2
(X = Cl, Br; L = PR3, R = Me,Et,Ph) or
NiI2(PhNH2)4 as catalyst precursors at 150-180°C and 20 bar. The aniline solvent was simultaneously converted to diphenylurea [107]: RC6H4N02 + 3C0 + 2PhNH2
-
RC6H4NH2 + CO(NHPh)2 + 2C02
Nitrobenzene and para-substituted nitrobenzenes were reduced by CO with good yields to anilines in the presence of a Pd(OAc)2 + PPh3
(1:4) catalyst in aqueous AcOH. The analogous reduction of
PhN02 in BuOH + H2S04
(1:5) gave p-HOC6H4NH2 [1081.
7. Miscellaneous Reductive Transformationsof CO and CO2 The formation of MeOH from CO and H20 is catalyzed by Mo(C0)6 at temperatures below 15O'C
[1091. The reduction of CO or CO2 with Everitt's salt (K2Fe[Fe(CN)61) to methanol (see A.S. 1985 refs. 79,80) could be performed in a catalytic manner by reducing the Prussian blue (formed in the stoichiometric reaction) electrochemically and using for this a commercial solar cell as energy source [llO]. Electrocatalytic reduction of CO2 to MeOH at an Everitt's salt-mediated electrode in EtOH solution in the presence of 1,2-dihydroxybenzene-3,5-disulfonato
(tiron) ferrate(II1) has
been studied. The formation of an intermediate Fe(III)-tironethyl formate complex was established 11111. The reduction of CO2 to MeOH on Pt electrodes modified with Everitt's salt was studied in the presence of different Fe and Cr complexes as homogeneous catalysts. Highest current efficiency was achieved with [112]. Methyl formate coordinated to the metal [(H20)(C204)2Cr1was proposed as an intermediate [113]. Carbon monoxide and carbon dioxide were electrochemically reduced to MeOH in the presence of the following metal complexes 3as homogeneous catalysts: Fe(CN)5(H20) , [Cr(C204)2(H20)21-, CrC15(H20)2-, FeF5(H20)2-, Fe(CN)5(NH3)3-, and 4,5-dihydroxy-1,3benzenedisulfonatoiron(II1).
Best current efficiency was 100% for
CO and 16% for CO2 [114]. Controlled potential electrolysis of a DMF solution containing [Fe4S4(SCH2Ph)4]2- under CO2 resulted in the formation of formate and phenylacetate. In the presence of excess PhCH2SH the yield of phenylacetate increased and the cubane
References p. 5 14
420 structure
of the catalyst
was preserved
during
a longer
period
11151.
The homogeneous studied
with
Maximum
activity
photocatalytic
was
achieved
[116]. Carbon
complexes irradiation
with
light
electron
transfer
numbers
ligands were
in MeCN
as catalyst.
The effective
reduced
to formate
mediator
11181.
by Ni and Co complexes investigated.
[119]. Electropolymerized
catalyze
of
to colloid-associated
as electron
+ H20 was
under
composed
tris(bipyrazine)RuiII)
!bpz)3Ruf
Rh(bpy)3C13
of the two
to methane
system
was electrochemically
observed complex
t~~raaZaannUkne
donor,
from
as photocatalysts. ratio
be reduced
of CO2 to CO catalyzed
reduction
of macrocyclic over
could
in an aqueous
colloid
took place
i1171. Carbon dioxide co2 in aqueous solution using Cathodic
of CO2 to CO was
a 1:l molar
as electron
and a Ru metal
as senzitier,
with
dioxide
visible
triethanolamine
NaHC03,
reduction
5H20 and Re(C0)3(bpy)Cl
Rh(bpy)3C12.
the reduction
High
turn-
films of a
Ni
of CO2 to formate
[1201. Reaction formamide HCaONa
nf Et2NH
selectively
as additive
with
CO2 gives
tetraethylurea
PdC12(MeCN)2
already
+ Et2NH
co2
with
at room
-
as catalyst
temperature
Et2KNEt2
and diethyland PPh3 or
and 1 bar:
+ Et2NCH0
d This
is a reductive
pressure
III. Hydrogenation 1.
transformation
Catalytic sition-metal
and Reduction
H/D exchange
( 7 6-C6H6)Re(PPh3)2H C6D6
hydrogens
its metal-hydride
diation
of the trihydrides
in C6D6
solution
solvent,
with
the hydride
is promoted
at 200°C.
this process
catalyzes
and aromatic
and meta
exchange
in alcohols
(Zr, Nb, Ta) alkoxides
are the intermediatesof
ortho
H2 and high
D and T Labeling
H Exchange, -
between
of CO2 not using
[121].
hydrocarbons,
ligand
the H/D exchange
and between
ligands.
with
UV light
causes
C6D6
and the
The complex
the D source
( 3 5-C5Me5)RuH3(PR3)
ligands
compounds
[1221. The complex
if irradiated
of its PPh3
by early-tran-
Carbonyl
does
not
Irra-
(PR3 = PPrl3, PPh3)
H/D exchange
and the coordinated
[1231.
between
phosphine
the [124].
421
The soluble iridium polyhydride H5Ir(PPrij2 catalyzes the H/D exchange between C6D6 and CH4 in the presence of neohexene at 80°C. The deuteration of methane needs several days and is preceded by the conversion of all neohexene into neohexane and by H/D exchange between C6D6 and both the hydride ligands and all the hydrogens on the phosphine ligands [125]. See also [71.
2. Hydrogenation of Olefins a)
Fe, Ru, and OS catalysts
Hydrogenation of cyclohexene is catalyzed by [CpFe(C0)212 at 17OC and 6 bar with a turnover of 16 h-1. No mononuclear intermediates are formed during this reaction because if hydrogenation is performed with a mixture of [CpFe(C0)212 and Iq-C5Me5)Fe(C0)212 no mixed-ligand dinuclear complex can be found in the product [126]. The PhLi + Fe4S4C1i- (6:l) system catalyzes the hydrogenation of terminal double bonds of monoenes and dienes with H2 [127]. Partial hydrogenation of refined canola oil with Ru(PPh3)3C12 as catalyst was examined. This complex catalyst was about as effective as heterogeneous Ni catalysts in producing hydrogenated fats with a low trans-fatty acid content [1283. The bis(imido) clusters Ru~(NAIY)~(CO)~
(Ar = Ph, p-substituted phenyls) catalyze
the hydrogenation of olefins under 3 bar H2 at 98OC. The clusters probably remain intact during the catalytic cycle [1291. The anionic ruthenium cluster [Ru3( /J-NCO) (CO),,]- was shown to catalyze the hydrogenation of terminal, unactivated olefins. The analogous [HRU~(CO)~~]- cluster was inactive but catalysis could be promoted also by Cl- or Br- in place of NCO- [1301. The tetraruthenium clusters H4Ru4(C0)12 and H4Ru4(C0)10(PPh3)2 were anchored on polymer supports modified by tertiary phosphine groups and used as catalysts for the hydrogenation of 1-hexene [1311. Three types of Ru carbonyl complexes anchored to Si02 via phosphine ligands: H,Ru4(CO)8(PPh2C2H,-SIL)4,
Ru3(CO)g(PPh2C2H4-SIL)3, and RUG
(PPh2C2H4-SIL) were used as catalysts for the hydrogenation of ethene at 70°C. Decarbonylation of the anchored complexes occurred only above 18O'C [132].
References p. 5 14
422 The orthometalated lysts
for olefin
high:
it was equivalent
of
found
and superior
of O2 enhanced
amounts
ligand
into OPPh3
to be cata-
(22) was especially
to that of HRu(PPh3)3Cl
Small
one PPh3
(19-22) were Activity
hydrogenation.
that of Rh(PPh3)3Cl. transforming
complexes
to
its activity
by
[1331.
tOPhI
(OPW2 19
20
Pd [P(OPh)3lCl O,p’ tOPhI
22
21 Hydrogenation catalyzed numbers with
CpNiOs3(CL-H)3(CO)8L
lated
An allylic
from the reaction
See also
and 3,3-dimethyl
Dienes
were
clusters complex mixture
and 3 bar with hydrogenated
is
turnover
to monoenes
(L = CO, Ph2PH,
derived
butene
P(C6H4Me-o)3
from the diene
was iso-
11351.
[44, 187, 2031.
Co, Rh, and Ir Catalysts Selective
with
[134].
anhydride at 60-80°C
by OS~(NCO)(CO)~~ of 3-8/day
as catalysts.
b)
of maleic
hydrogenation
of citral
cyanoethylenediaminocobalt
Maleic
and
fumaric
dicarboxylic succinic
first
acid by vitamin
ing methyl
esters
way to methyl
catalyst
acid were
acid was
reduced reduced
B12s
of the three
succinate
to citronella1
[138].
in MeOH/H20
to succinic to fumaric
(cob(l)alamin) acids were
was achieved at 25'C
acid,
[1361.
acetylene-
acid and then to
11371. The correspond-
also
reduced
in a similar
423 The complexes
olefins
[139].
tene with
cyclohexene, genation
were
determined
labile
tion
of Me sorbate
earlier was
was
were
were
also
in the presence of the mixed
genated
the acrylic
carboxylic
acid
less active
complex
[143].
thus
system
saturated process
ketones
shown
systems
to catalyze
and esters
is both chemically
Rhodium(I) as catalyst
polymeric
quinoxaline-Rh hydrogenation
dienes complex
silica-supported
and the phosphines of E-toluenesulfonic hydrogenation
of alkenes
were
with
attained
active
than their
References p. 5 14
P/Rh
under ratios
homogeneous
of the
and RhC12(2-methylhydrogenacomplex
the cyclooctene
chloride
formed
in a two-phase
the hydrogenation
of
a,P
at the C=C bonds. controlled
-un-
The
[1441.
complexes
were
used
alkenes
and alkanes
[1451. A polyphenyl-
and used
found mild
to alkanes
as catalyst
and bromopropene
complexes
prepared
from
for the 11461. Ph(COD)(acac
(n = 1,3) in the presence
(Et0)3Si(CH2)nPPh2 acid were
the hydro-
[(C8H17)3NMel+[RhC141-
butyraldehyde Rh(1)
hydro-
of terminal
was prepared
of olefins,
involves
by transesterifi-
activity
phosphinocarborane
to monoenes
in acetone
liberating
than
selectively
[1411.
be per-
The allylrhodium
and diffusion
for the hydrogenation
and conjugated
Cationic
was
could
in the homogeneous
was examined.
ion pair
of Me
of Me sorbate
followed
substrate
was Me
Rh(CO)(PPh3)2C1
acids
11421. The catalytic
The solvated
product
as catalyst
from RhC13. 3H20 and methyltrioctylammonium liquid
Main
The mechanism
ligand
catalytic
Hydrogena-
the hydrogenation
acrylic
systems
Hydro-
to the
of Me trans-3-hexenoate
+ 2-alkylaminopyridine
olefins
[1401.
The complexes
catalyzed
+ 2-alkylaminopyridine
tion of different provided
amounts
of a base.
acid
127).
Rh(PPh3)3C1,
as catalysts.
anhydride
[RhCl(cycloocteneJ212 allyl)
at 100°C with
RhC1(PPh3)2(Ph2POCOCH=CMe2)
solution
with
in this case
substituted
genation
ref.
and this was attributed
for the hydrogenation
of highly
by using
of
formed.
which
inactive
has
that of the hydrogenation 1984,
of
of l-hep-
as catalyst
complex
studied
[Rh(NBD)(dpe)l(PF6)
Hydrogenation
hydrogenation
(see A.S.
faster
but significant
and Me hexanoate
cation
with
and HRh(CO)(PPh3)3
trans-2-hexenoate
formed
of homogeneous
dihydro-olefin
[Rh(NBD)C112,
2-amino-1,3,2-di-
for the hydrogenation
[DPPA = HN(CH2CH2PPh2)21
of 1-heptene
linoleate
as catalysts
and compared
more
and
used
The kinetics
Rh(DPPA)Cl
been determined
(L = different
[RhCl(CO)L12
oxaphosphorinanes)
to be efficient conditions.
Highest
of 2; such catalysts analogues
[147].
catalysts
for
activities
were more
424 Homogeneous and
hydrogenation
Ir(1) complexes
(E = P, As) was concluded plexes
that
of the terdentate
the enthalpies
step
of a ligating was
of formation
shown
show
group,
to direct
e.g.
show
olefin
(23) gave
effect
was
14-electron
this
of
!1451. The
of H 2 in case of as solvent onto
and CH2C12
the directing
only
group.
species
Thus,
for
This very pronounced
for the 12-electron
like Rh(PPh,),Cl
"IrL2"
did not
[149].
‘j-
23 [133,
com-
of activation
\c *
catalytic
selectivity
it was
on an olefinic
(24) in 99.9% yield.
characteristic
HO
See also
experiments
relationship
the addition
containing
system:
HN(CH2CH2EPh212
OH or COOMe
the face of the molecule
by Rh!I!
of the dihydride
an inverse
as catalyst
directing
ligands on kinetic
[Ir(COD)(PCy3)(py)j!PFUj
example,
catalyzed
(M = Rh I Ir) and the enthalpies
H2M(L)Cl
substrate
Based
investigated.
the rate-determining presence
of cyclohexene
24
216, 2171.
c) Ni, Pd, and Pt catalysts The reaction been
found
product
to be an active
hydrogenation
of alkenes
to the catalyst: took place
in their
on Pd(acacj2
was
nylpyridine)
were
catalysts
studied reduced
[151j.
only
in THF has
for catalytic
groups
were
stoichiometric
poisonous reduction
prepared
and used
active
catalysts
of Pd(I1)
or H2 and tested and acetylenic than Pd black
the same conditions
on phosphinated
for hydrogenation
based
poly(2qi-
as catalysts These
1152, 1531. catalyst
1,3- and
into cyclohexene
catalyst
with
alcohols.
on a polyaziridine-PdC12
disproportionated Pd(I1)
Complexes
by NaBH4
were more
was hydrogenated
A heterogenized was
catalyst Nitro
of hydrogenation
of olefinic
50°C and 5 bar H2. Under hexadienes
presence
of formation
for the hydrogenation
lohexene
homogeneous
and alkynes.
and LiA1H4
[150].
The mechanism
complex
of nickelocene
Cycat
1,4-cyclo-
and benzene
!154].
montmorillonite
of olefins
and acetylenes.
425 The results swelling
obtained
in various
properties
Polymer-supported
Pd(0)
and Pt(O)
reacting
CpPd( q3-C,H,)
and used
for the hydrogenation
catalysts
prepared
or Pt(COD)2
d)
1133, 135,
Other
catalysts
with
were
prepared
by
4,4'-diisocyanobiphenyl
found
lenes.
In some cases
phenylacetylene
into
Asymmetric -
specific
and alkynes.
The Pd
to the about
as active
Rh(I1)
moderately
can be observed:
into cyclooctene
containing
(R =CHOHPh)
hydrogenation
1,3-
and di-
[1571.
Addition
bridging
was
of prochiral was
observed
tested olefinic
for
acids.
Practimixture
but resulted
homogeneous
mandelate as catalyst
and the reaction
of PPh3 or chelating
the activity
enantioselective
and acety-
of Olefins
complex
no enantioselectivity
decreased
selectivities
Z?&$'Ph2
diolefins
1,2,3,4_tetraphenylbutane
[R~(oocR)~(H~o)]~
was not homogeneous.
the chelated
of olefins,
are transformed
Hydrogenation
The dimeric
the asymmetric
containing
the hydrogenation
and 1,5-cyclooctadienes
ficantly
the
Pd [1561.
complexes
catalyze
cally
with
Metals
Zirconium(II1)
ligands
in accord
1941.
moiety
3.
were [1551.
of alkenes
in this way were
as PdIC or polystyrene-bound See also
solvents
of montmorillonite
amines
signi-
in the formation
catalyst
of a
(0.~. up to 15%)
[158]. A practical l,l'-binaphthyls been
developed
synthesis (BINAPs,
of
(RI- or
(S)-2,2'-bis(diarylphosphino>-
25; Ar = Ph, p-MeC6H4,
ptBuC6H4)
[159].
PAr2 25 PAr2
References p. 5 14
25a
has
426 The degree
of asymmetric
(-)-methyl
esters
[Rh(dipamp)l+ of the
complexes
rnenthylgroup
butenoic ence
induction
acid
was
diphosphine
(-)-norphos were
dependent
were
from
The best
[1611.
Rh(I>-chiral
(90%) of the desired with
in the pres-
obtained
derivatives
(26) using
as catalysts.
(an artificial
(27) as ligand
with
and the ligand
derivatives
systems
L,L-enantiomer
(R)-prophos
x
acid
and L,D aspartame phosphine
01-acylamino-2-
and several
were
The dehydroaspartame
to L,L-
of
hydrogenated
results
by
on the configuration
[Rh(COD)Cl12
(Z)- a-acetylamino-2-butenoic (115)
and different
was obtained
ester
formed
ligands.
hydrogenated
yield
strongly
and its methyl
the substrate
of (+I- and catalyzed
The Z- and E-isomers
[160].
of in situ catalysts
chiral
in hydrogenation
of 3-hydroxy-2-methylenebutyrate
Pa/C
Highest sweetener:
11621.
I
COOMe
HOOC R =CHO
26,
or
The mono-dehydro different
chiral
COOCHZPh
Leu-enkephalin
Rh(1)
complexes
[Rh(dipamp)(COD)](BF4) 68%
CR)-product
product metric
leads to 93%
was obtained.
is mainly induction
in the substrate
controled
This
were
prepared
(S)-product shows
due to the two chiral
Application while
of the
and overcomes
aminoacids
using of
with Rh(BPPM)Cl
that chirality
by the catalyst
already
asympresent
[163].
’
CONH-CONH-CONH
The water
(28) was hydrogenated
as catalysts.
soluble from
chiral
the parent
in an aqueous-organic
“>lCO f .k
ditertiary compounds
two-phase
system
phosphines
COOMe
28
(29) and
(30)
by sulfonation
and used
for the asymmetric
hydro-
427 genation with
of
Rh(1)
ci-acetamido complexes
lower
than those
ganic
solvents;
cinnamic
acid and some of its derivatives Optical
as catalysts.
obtained
with
yields
the unsulfonated
the best value
was
were
somewhat
phosphines
in or-
88% [1641.
H PAr2
Ar =
PAr2 n=Oorl 30 The new chiral ligand Rh(1)
biphosphine
in the asymmetric complexes
analogue
hydrogenation
as catalyst.
(32) was prepared
metric
hydrogenation
plexes
as catalysts
(31) was prepared
Best
of dehydro
of dehydroamino
o.y. was
and used
and used
90%
as chiral
acids
[1651. ligand
N-acylaminoacids
as with
The DIOP in the asym-
with
Rh(1)
com-
11661. H Me2C
!
I0
P(C6H4Me-312
‘0 T
P(C6H4Me
-312
H 32
31 The water-soluble been prepared
and were
tion of dehydro strongly
chiral used
aminoacids
decreased
in water
was noted
chiral
[1671.
when
dipamp
(33) and
(34) have
in the asymmetric
or EtOH.
the enantioselectivity
no such effect liqands
diphosphines
as ligands
hydrogena-
Unexpectedly,
of these
or norphos
water
catalysts
while
(115) were used
PPh2 PPh2 H
33
References
p. 5 I4
34,
n = 16 or
42
as
428 The chiral cose
and used
phosphines
as ligands
for the asymmetric
cc-acetamidocinnamic
acid and
Phosphine
(35) gave
catalyst. than
(36) were
(35) and
itaconic
prepared
from D-glu-
hydrogenation
acid with
significantly
of
[Rh(COD)C112
higher
optical
as
yields
(36) [168].
The chiral as ligands with
bis(tertiary
The best amido
optical
cinnamic
of the type pared
[169].
as ligands
were
achieved
substrate:catalyst
R = CH2NH2
(37) and
of unsaturated
(38) were
carboxylic
used
acids
prepared
Several
(R = different
as catalysts
36,
in situ from [Rh(COD)Clj2. --(70%) was obtained in the case of d-acetbistertiary
In most
(up to 99.5%) could
phosphines
and acyl groups)
were
hydrogenation
acid derivatives
(PP = 39).
ratio
chiral
alkyl
in the asymmetric
cl-(acylamino)acrylic
complexes yields
yield
(39)
and used
ferent
complexes
acid
R =CN
phosphines)
in the hydrogenation
Rh(I)-phosphine
35,
with
cases
even under
be increased
of dif-
[Rh(COD)(PP) I+
very
high optical
pressure.
up till
pre-
The
50.000
[1701.
0 (men)2P (men)2
P
The water used
soluble
Rh(1)
for the hydrogenation
cinnamic and
0
acid
furnished
in water
complex
of the
solution.
(40) has been prepared
sodium
salt of
The catalyst
(S)-N-acetylphenylalanine
was highly
in 90% o.y.
(BF4 );
and
d -acetylaminoactive
11711.
40
429
Optical of
yields
up to 100% were
C(-acetylaminocinnamic
acid and
obtained
in the hydrogenation
its methyl
ester
in the presence
of Rh complexes
of 3,4-(R,R)-bis(diphenylphosphino)pyrrolidine,
bound
(41). The catalyst
to silica
could
be reused
three
times
[172].
Y p+
-O\
41
-NH-i&-Nx)Rh(COD)*
-07Si-fCH213 -0
H
The chiral were
prepared
olefins
tioselectivity itaconic
sugar diphenylphosphinite
and used
of prochiral
acid
Phq
as ligands
with
in the asymmetric
[Rh(COD)Cl12
was obtained
with
derivatives
(42) and
(43)
hydrogenation
as catalyst.
Complete
(43) in the hydrogenation
enan-
of
[1731.
X0
0
42 The air-stable starting
N-acyldehydro-
a-amino
in a catalyst
selectivity lost
than
its activity
bisphosphinites
and the cationic
as catalyst
Immobilizing
[1741.
resulted
chiral
from D-glucose
(L = 44a) was used
ed
43
acids.
Optical
yields
the homogeneous
catalyst.
of 94-99%
were
cation
showed
If recycled
R
achiev-
enantio-
it slowly
[1751.
R’
44 a
H
OPh
44 b
OMQ
H
44 c
OPh
H
of
exchanger
a better
but not its enantioselectivity
I
Rh(L)WD)+
hydrogenation
on an organic
is some cases
prepared
complex
for the asymmetric
this complex which
(44) were rhodium
A polymeric
phosphine
tetraethylenepentamine plexes
of this
lysts acid
was prepared
and the chiral
copolymer
with
for the asymmetric
NiCl2
from diethyl
tartrate,
bisphosphinite
and CoC12 were
hydrogenation
of
(45). Comused
as cata-
d -acetylaminocinnamic
[1761. ,COOEt
Ph2P0, CH
45
I Ph2PO The new chiral pared. lysts
Cationic
o.y.
92%)
‘COOEt
aminophosphine
Rh complexes
for the asymmetric
(highest 53%)
AH
phosphinites
of these
ligands
hydrogenation
(46-49) were were
used
of dehydroamino
[177] or of (50) to pantolactone
pre-
as cataacids
(51)
(best o.y.
[178].
Me -CH-0PPh2
,’ H
I
tH20pph2 CH-NPPh2
Ph-CH-NPPh2
c,, N I
I
I
I
R
R’
Me
Rh(1)
of dehydro
complexes used
‘i’
COOR
PPh2 49
51
of the chiral
as catalysts
amino
in some cases
n
48
50
(53) were
.’ .H
CH20PR2
PR2
47
46
H :
Ph2PO
acids.
Optical
the arsine
phosphines
and arsines
for the enantioselective
proved
yields
up to 94% were
to be the more
a
Ph’
,Ph E” E “’ Me
observed
selective
L1791. Me,
(52) and
hydrogenation
52,
E=P
53,
E= As
ligand
and
431 Asymmetric saturated SO-80°C
ketones
[180].
of cC,p -unsaturated
was achieved
and 40 bar
cyclobutene). rone
hydrogenation
with
Highest
o.y.
The chiral
for asymmetric
(62%) was obtained
Ru complexes
hydrogenation
o.y. was
26%
ing the enantiomers were
used
like
(56) or
at 23OC) 100%).
[1811.
of acetylated
The Ti complexes
yields
is useful
important
A-(R)-
ligand
the reaction
and optical
This new method
dehydroamino
for the asymmetric
and
styrene.
Highest
and catalysts acids.
Ru complexes
BINAP,
(54) and
hydrogenation was rather
were
generally
slow
bear-
(55), of enamides (2-6 days
excellent
(near
of various
[182].
A-
54
(58) and
as
used
for the synthesis
products
as catalysts Q-ethyl
at
in the case of pho-
The hexacoordinate
for the asymmetric
(57). Although
physiologically
as catalyst
~~Ru~(co)~[(-)-DIoP1~
(n = 2,3) were
of the chiral
as catalysts
chemical
trans-IIRuClL2
to
[L = trans-1,2-bis(diphenylphosphinomethy1)
Ru~(CO)~[OOC(CH~)~COO][(-)-DIOP]
Highest
ketones
(S)
(59) activated hydrogenation o.y. was
34%
with
- 55
BuLi were
of 2-ethyl
[183].
used
hexene-1
432
4.
Hydrogenation
of Dienes
Alkynetitanium
complexes
H2 and are catalyst Selective of PMe3 or
catalyze
Homogeneous
selective
fins,
dienes,
of olefins were
dienes
aldehydes
to unsaturated
from
BuMgBr
with
in the presence
(MeC5H4)2TiC12,
and LiA1(OBut)3H 11851.
The dinuclear
catalyzes
[1861.
the
Hydrogenation
and ketones,
Unsaturated
alcohols,
unsaturated
High selectivities
of dienes
aldehydes
of ole-
and hydroformylation
by HOsBr(CO)(PPh3)3.
in the hydrogenation
to alkenes.
obtained
react
of alkynes.
of COD at 50°C and 1 bar in the presence
is catalyzed
observed
alkynes
place
of cyclopentadiene
and conjugated alkynes,
takes
Ru~(COD)~(O~CCF~)~(H~O)
hydrogenation
of cyclooctene
systems
(n = O,l),
the hydrogenation complex
for the hydrogenation
to cis-olefins
(MeC5H4)2Ti(OPh)2_,Cln
Ru carboxylate
like Cp2Ti(PhCCPh)(PMe3)
precursors
hydrogenation [184].
and Alkynes
to monoenes
were
ketones
and of
hydrogenated
to saturated
mainly ketones
11871. Hydrogenation piperylene) gave was
of 4-methyl
using
K2;Co(CN)5]
4-methyl-2,6-nonadiene hydrogenated
Co(PPh3)3X products isomerized
to norbornene
different
CIDNP pair
(X = Cl,Br)
NBD dimers
[1891.
measurements, intermediate
by HCO(CO)~ both reactions
[190].
of
diamine)]
[188], Norbornadiene
and the tricycloheptane
to 2,4-dimethyl-1,3-pentadiene
2,4-dimethyl-2-pentene
(linear dimers
or K2[Co(CN)3(ethylene in 90% yield
+ BF3. Et20 catalysts were
nonatrienes
in 5-19%
(6Oj by yield.
Main
Tetramethylallene and hydrogenated
and HMn(C0)5. take place
is to
As supported
over
a common
by radical
433
al
60
Diphosphines
of the type
(n = 1,3) were
used
complexes
were
effective
octadiene
11911.
gave
complexes
which
were
active
with
tertiary
In some cases
(iBu)2AlH
[192].
from the ferrocenyl
thiother
ligand
catalyst
for the hydrogenation
octadiene
to cyclooctene
Several polymers
were
developed
Depending
be performed:
(depending
The catalysts tion
formed
was
found
of 1,3-cyclo-
[1931.
systems
based
on linear
or poly(ethyleneimine) hydrogenations
the following
as
in liquid
hydrogenations
could
on the ligand);
could
be separated
Ni - alkynes
to s-alkenes.
from the product
by ultrafiltra-
[194].
See also
5.
for selective
on the metal,
of acetyle-
Rh - aromatics (cyclohexanone from nhenol), suqars; nitro groups, C=N bonds, alkynes to -cis or trans
Pd - alkenes, alkenes
solution
amines
the resulting
(61) and K2PdC14
catalyst
like poly(vinylpyrrolidinone)
ligands phase.
in acetone
new homogeneous
of 1,3-cyclo-
The complex
to be a homogeneous
The
aliphatic
for the hydrogenation
to olefins.
with
on silica.
for hydrogenation
of PdC12
were
reduced
Rh complexes
catalysts
dienes
6’
SPri
(EtO)3Si(CH2),P(Ph)CH2CH2PPhZ
to immobilize
Reaction
nes or conjugated complexes
&
[146, 150, 156,
Hydrogenation
of Arenes
Hydrogenation 40-80°C
and 20-60
to cyclohexane
157, 2171.
of benzene bar
[195].
was carried
[196]. Naphthalene
and Heterocyclic
is catalyzed liquid-phase
out over
was hydrogenated
P.hC13.3H20 + methyltrioctylammonium in a two-liquid naphthalenes, mainly went
References
phase naphthols
system
partial
p. 5 I4
hydrogenolysis
by aqueous hydrogenation
rhodium
trichloride
Ru(OH)C13
chloride
(Aliquat
naphthoates
ring-chlorinated [1971. Phenol
were
at
of benzene at 20°C
at 30°C and 1 bar with
to give decalin-free
and ethyl
at the non-substituted
Compounds
a
336) catalyst
tetralin.
Methyl
hydrogenated
naphthalenes
was hydrogenated
underin the
434
presence
of catalysts
-soluble
polymers.
activated with
gave preferentially
complexes
and methyl
as catalysts proceeded
of poly(acrylic cyclohexanone
with
polyacrylic
acid,
methacrylate-maleic
for the hydrogenation
over
with wateracid)
(74%) along
[1981.
cyclohexanol Rhodium
on Rh and Pt complexes
the Rh complex
Thus,
by NaBH4
copolymer
based
furfuryl
alcohol
styrene-maleic
acid copolimer
of furfural.
acid
were
used
Hydrogenation
to tetrahydrofurfuryl
alcohol
[1991. See also
6.
[1941.
Hydrogenation
The anionic catalyze
of Carbonyl
group
6 carboxylates
the hydrogenation
50 bar. Activation anion-stabilized
Compounds
of dihydrogen dihydride
and ketones
was proposed
or dihydrogen
R
I HC -0::
(M = Cr,W,Mo)
M(C0)5(0Ac)-
of aldehydes
at 125OC and
to proceed
complex
,+, i ,;M(CO);
(62)
over
the
[ 2001.
62
‘..A ,’
AI
Acetaldehyde and
was hydrogenated
445 bar using
[HR~3(C0)1~1-
[HRu(CO)~~-
proved
A similar
was
in the synthesis
found
and 500 bar
[201].
as catalyst.
to be much
reaction.
activity
of methanol
Hydrogenation
investigated.
HCl the selectivity
with
complexes
RuC12[Ph2P(CH2)nPPh2]
catalysts
was
bar.
Linear
acetone
tested
olefins
could
be
saturated
were
from
99%
were
gas at 230°C
group
of citral
complexes
as cata-
[202]. The activity
hydrogenated
only with
for this
and in the presence
at 65-95OC but cyclic
the most to prooyl
reduced
of
of the
as hydrogenation
substrates
was hydrogenated
hydride
the two complexes
synthesis
Ru(II)-PPh3
(n = 1,2,3)
easily
or cinnamaldehyde aldehydes
was
different
hydrogenated
(n=3). Propionaldehyde tonaldehyde
with
between
solvents
CO + H2 at 180°C
as a catalyst
of the carbonyl
In protic
for dienol
with
The trinuclear
less active
difference
(3,7-dimethyl-2,6-octadienal) lystswas
to ethanol
active
and lo-17
olefins
and
catalyst
alcohol,
and cro-
to the corresponding
[203]. When -trans-4-tert-butylcyclohexanol
was
435 subjected
to 35 bar H2 at 145OC
amount
(63) in toluene,
cis
of
(25.2 mole
%) and trans
corresponding shows
that
alcohol described
(69.7 mole
cyclohexanone
(5.0 mole
(63) reversibly
dehydrogenation. as
in the presence
of a catalytic
a constant-composition
catalyzes Complex
mixture
%) alcohols
%) was formed. ketone
This
(AS 1985,
as the result
hydrogenation
(63) was earlier
[(?14-Ph4C4CO)(CO)2Ru]2
of the
as well
and
erroneously
ref.
97)
[204].
63
Hydrogenation use of several
of aldehydes
MX(OCOR')(CO)(PPh3)2
involving
involving ligand
at 150°C
HMX(CO)(PR3)2
Hydrogenation
of Ru(CO)~(PBU~)~(ACO)~
reaction
is performed
nium and
partly
carbonyl
in MeOH
transformed
homogeneous
Rh + MeI catalysts decarbonylation
or
pro-
species
or
for the carboxylate
[205].
oxalate
at 180°C
gives methyl
and 130 bar in the
glycolate.
If the
the glycolate
as solvent,
glycol
[206].
is subseThe ruthe-
(A~O)~R~~(CC)~(PBU~)~V (Aco)4Ru4(CC)8(PBu3)2~ were
hydrogenation
H4Ru4(CO)8(PBu3)4
were
active
equilibrium
into ethylene
carboxylates
(AcO)~RU(CO)~(PBU~)~
cursor
and 30 bar. Mechanisms
in the catalysis
of dimethyl
by the
R' = Me,Et,Cy,tBu,
as catalytically
presence
quently
R = Ph,Cy;
a bidentate-monodentate
as a key step
was achieved
of the type HMX(CO)(PR3)3
(X = Cl,Br;
CH2C1,CHC12, CF2C1,CF3) posed
and ketones
Ru and OS complexes
identified
of AcOH [207].
benzylic
to EtOAc
using
In the presence
carboxylic
and reduction
as intermediates
acids
by synthesis
in the
the catalyst
pre-
of Ru + MeI or
undergo
reduction,
gas at 220°C
or
and 430
bar:
Ph-+COOH
The ratio
__c
+ Ph-+I
of the two products
acid on the metal:
Referencesp. 514
Ph-+CH3
Ru generally
depends
favors
on the structure
reduction
of the
and Rh decar-
436 Benzoic
bonylation. tions with
[2081.
hand
if
(65) and the latter with
lactone
gave
(64) was compound
(67) was
to toluene
of the cyclic
the lactone
first
reduced
(66) in 99% yield. to the diol
in toluene
and benzalacetone
!reflux)
as H acceptor,
in 88% yield
obtained
such condi-
(64: at 160°C
by LiA1H4
the
[209].
6Me
bMe
64
under
anhydride
was dehydrogenated
as catalyst
H2Ru(PPh3)4
isomeric
is reduced
as catalyst
Ru2Clq(dppb)3
On the other
acid
Hydrogenation
67
bMe
OMe
65
The kinetics in py has been Co and showed
of hydrogenation
a maximum
with
Enantioselectivity catalyst enced
systems
used
by the addition
fects were
explained
Rh complexes ketones
dextrin
dextrin;
and stereoselectivity
of suitable
aldehydes
to give
active react
quantities
hydrocarbons
the favorable
effect
of
in
of Rh-phosphine could
These
12111. Aryl
[Rh(HD)C1j2 Yields
with and
ef-
alkyl H2 in p -cycle-
are much
or in the presence p -cyclodextrin
be influ-
or dihydrido
in THF solution
yields.
order
!2101.
as additives.
species
by Co(dqm)2
to be first
of monohydrido
of
in high
of any cyclodextrin
catalyzed
of ketones
bases
by the formation
of catalytic
in the absence
found
py concentration
for hydrogenation
as catalytically
and aromatic
the presence
of benzil
The rate was
determined.
of
lower
cl-cyclo-
is probably
due
437 to the fact that
it forms
D-(-)-Pantolactone metric from
hydrogenation [Rh(COD)C1]2
and BPPM
(68) were
asymmetric
hydrogenation
efficient
could
[213].
prepared
ligand
be achieved
with
was
as ligands 64-72% fluence
hydrogenation complexes
R=
68b,
R = -CONHPh
68c,
R=
center
[iPr2P(CH2)4PPri]
-COOBut
the chiral a-amino
R‘ = Me,
;
PCY2
)
References
p. 5 I4
of hydrogenation
(benzylideneacetone prepared
drastically
of phosphine
12151.
PCY2
PCY2 71b
The selectivity
excess
6%
PhCH2
XT- 0 _.-
71 a
phosphines
if an achiral
R’
0
PCY2
catalysts
no in-
70
o-..
complex
(70) in
the o.y. was only
69
Ph
(71)
RkHCONHkHCOOMe * t
-
*
esters
had almost
of the reaction:
was used,
esters
phosphines
of the substrate
OH
7’COOMe RCOCONHCH
compounds
The
MeS02-
of N- (a-ketoacyl)-a-amino
containing
N-( a-hydroxyacyl)-
The chiral
R = Me,
as catalysts.
92% enantioselectivity
68a,
on the diastereoselectivity
diphosphine
for the same
[214].
produced
o.y.
in situ -pyrrolidinebis-
as ligands
complexes
[2121.
by the asym-
formed
The new chiral
Rh(1)
A Rh(1)
yield
the catalyst
(68~) with which
PPh2
Asymmetric
the substrate
in 92-98%
and used
CYZP,
(69) with
with
of (50) using
phosphines
most
a complex
(51) was prepared
of cC,p -unsaturated
or cinnamaldehyde)
with
in situ from [Ir(COD)(OMe)12 -changed with the P/Ir ratio. When
was used,
carbonyl
Ir-phosphine and a twofold
the C=C bond was hydrogenated,
with
438
a P/Ir
ratio
selectivity
of 10 the carbonyl 12161.
the hydrogenation hyde
The Ir(II1)
of phenylacetylene
to hydrocinnamaldehyde
See also
[218].
alkenes
benzothiazoline
!219].
is catalyzed
nitro
groups
are not hydrogenated
genation
catalysts;
the best
of 4-vinylpyridine
PhMeCHNH2
gave
was
with
12221.
The Mo(VI)
com-
using
Hydro-
Pd com-
increased of the
by photochemical
grafting
hydrogena-
of PdC12
+ !S)-
(72b) containing
hydrolysis
72a,
R
72 b,
R = NH2
transformed
N02 HCI
2231.
Hydrogenations complexes
[ (MeCP)Mo( I-L-S) (P-SH) I, for the hydrogenation at room
[2201.
for E-C1C6H4NH2
q
by H2
and nitrile
[2211. Asymmetric
Acidic
of
at ambient
compounds
Complexing
HCl the amine
(72b) into L-lysine
Miscellaneous
investigated
was obtained
in 11% excess.
was pre-
isoquinoline)
carbonyl
as catalysts.
its L-(-Jenantiomer
1101, 194,
nitro
(72a) in the presence
workup
The com-
to be the most
the same conditions
onto polyethylene
after
found
in DMF solution
and selectivity
support
for the hydro-
for the hydrogenation
Formyl,
under
tion of 3-nitrocaprolactam
strates
[217:.
pressure.
(L = quinoline,
supports
activity,
was
of aromatic
of p-nitrochlorobenzene
the stability,
as catalysts
at elevated
compounds
DMF solution.
on polymeric
used
catalyst
by trans-PdC12L2
in alkaline
8.
at 60°C
[Rh2C12(COD!2(phenazine)l
Hydrogenation
plexes
See also
100%
and of cinnamalde-
alcohol
as ligand
complex
as homogeneous
and aromatic
conditions
were
to aniline
The Rh(1)
and used
plexes
almost
catalyzed
Compounds
0x0 complexes
of nitrobenzene
containing
pared
to styrene
and cinnamyl
of Nitro
Rhenium(V) genation plex
with
[Ir(phen)C12jCl
[19,44,146,178,187,194,199,492].
7. Hydrogenation
active
group was reduced complex
[(MeCp)Mo( u-S)12S2CH2 could
be used
of a series
temperature
and
as homogeneous
catalysts
of nitrogen-containing
and 2-3 bar.
Phenyl
aside
subwas convert-
439
ed to aniline,
azo compounds
phenylhydroxylamines hydrazine.
The C=N double
isocyanates
were
is uncertain dimerized
to hydrazines,
to anilines, bonds
in imines,
also hydrogenated.
as catalyst
[H3Ru4(CO)121of the catalyst
to the corresponding
precursor
at 120°C
formamides
-
The role
R
I R = Me, Et, nPr
a
a
74
The olefinic + CoC12)
hydrogenated
sultam-imide
(75) was
and catalytically
to give
discrimination selectivity
and 50 bar.
of the isocyanates
R/N\C/N\C/H
73
(LiA1H4
of
[224].
I
+ H2
be reductively
H2 in the presence
the hydrogenation
and
of the reaction
(73) could
H ZR-N=C=O
isothiocyanates
(74) with
is probably
and
to 1,2-diphenyl-
The mechanism
[2231. N-Alkylisocyanates
to N-formylureas
nitrobenzenes
azoxybenzene
(76) and
favored
(77). In all cases
the formation
was obtained
with
stoichiometrically
[Ir(COD)(PCy3)]+PFi
of
or Pd/C
diastereoface
(76); highest
the heterogeneous
diastereo-
catalytic
system
[225].
4
Pr
76
I\ ‘H
Na
inepr
+
502
75 The chiral (78) with Optical
References
purity
p. 5 I4
glycine
(79) was prepared
D 2 in the presence of the product
of catalytic was about
by the hydrogenolysis PdC12 80%
in D20/TKF
[226].
of
at 25OC.
440
H
Ph coo-
_ 0 Br
79
78 Uranium
hydride
PhN02
to azoxy-
PhPh,
and Ph3AsO of added
UH3 reduces
to Ph3As
in boiling
and the sensitivity synthetic
reagent i194,
towards
oxygen
also
9.
Dehydrogenation Cycloalkanes
were
dehydrogenated
for these
secondary
or allylic
aldehydes
was achieved
R R’
+
with
hydrogen
_
Ruthenium
ally1
complexes
cycle
1229 I.
with
energy
under
of
Cc ,p -unsaturated
as catalyst
R
proposed
0
z
and ally1
conversion
+ C3Hfj
as intermediates
photoirratiation.
in all cases;
+ co2
of iPrOH
Ir, Rh, Pt, and Ru complexes
than unit
"photo-thermal
were
Dehydrogenation
SnC12. 2H20 as catalyst was higher
or
acceptor:
-0COOMe
catalytic
unsaturation
Dehydrogenation
to ketones
H2Ru(PPh3)4
and arenes
by
coordinative
[2281.
R’
investigated
substrates UH3 as a
to cycloalkenes catalytically
Multiple
reactions
alcohols
as
carbonate
OH
do not recommend
and in some cases
iH21r~Me2C0~,~PPh3~,1~Sb~6)'
t
in the absence
organic
1971.
stoichiometrically
methyl
against
to PhH and to azobenzene,
12271.
See
was necessary
azoxybenzene
THF or at 130-170°C
The low reactivity
solvent.
(X = Cl,Br,I)
PhX
and azobenzene,
efficiency"
combined
efficiency
(iridium)
was
was
with
Quantum
in one case
of the
to acetone
larger
even
the
than one
[2301. Dehydrogenation 200°C
by the black
and AlEt3.
of tetralin solid
The catalyst
to naphthalene
formed
from CoCO3
contains
tetraline
is catalyzed
(suspended
at
in tetralin)
and naphthalene
which
441 from
can be extracted
it with
is catalytically
inactive.
hanced
Rh(PPh3)3C1
alone
by adding [231].
Et20;
The activity which,
The Co porphyrins
the dehydrogenation
the residue
of the system
however,
(80) were
of hydroquinone
of this
can be en-
is inactive
tested
extraction
with AlM3
as catalysts
for
[233].
80 R = Me,
Et
R’= H, Me, OMe, N02,
diols
Dehydrogenation
of unsymmetrically
is catalyzed
by Ru- or Rh-phosphine
ence
of H-acceptors
nant
products
tuted
are
[235] were
catalysts.
Using
induction
could
in the pres-
ketones.
The predomi-
y -1actones
(82), respectively. found
(81) and 7 -substi-
H2Ru(PPh3)4
to be the most
the corresponding be achieved
1,4- and 1,5-
complexes
O:,p -unsaturated
p-substituted
6 -1actones
HRh(PPh3)4
like
substituted
NMe2
[234] and
active
complexes
and selective
of DIOP
some optical
[234-2361. Me
OH
Me
OH
0
81
c 0 Me
Me Me
Me OH OH
Primary simultaneous
-
and secondary ligation
Dehydrogenation from amine
References p. 5 I4
amines
react
with
and dehydrogenation
2 (P)Fe(III)Cl+ 5 RNH2 -
transfer
a2
Fe(II1)
porphyrins
(P = porphyrin
ligand):
2 (P)Fe(II)(H@2 + R'CH=NH+ 2 m$l-
starts nitrogen
by reversible
outer-sphere
to the porphyrin
ring.
by
electron
The reaction
442 models
the monoamine
See also
1209,
10. Hydrogen
a)
239,
ne-2
of
transfer
resulted
No photoreaction Transfer
by iPrOH
triene
2-cyclohexene-l-01 HCo[PPh(OEt),]4
also
is methyl
under
hexene-1
linoleate
or hexe-
to methyl
linoleate
which
is transformed
H-transfer
is catalyzed
The active
of
by
catalyst
of free phosphonite
Some
as solvent,
in n-octane
Intramolecular
irradiation.
Addition
in a cyclo-
and H4Ru4(C0)12.
to give cyclohexanone
HCo[PPh(OEt)2]3.
[2371.
of cyclohexane
with
of methyl
place
[239].
light
in the formation
by RUDER
takes
the H-donor
into a conjugated
with
was observed
hydrogenation
is catalyzed
hydrogenation
in this case
P-450
bonds
(Bu4N)4[Pt2(P205H2)41
+ iPrOH mixture
[2381.
oleate
of cytochrome
Reactions
of C=C or C-C
Irradiation
and acetone.
function
2431.
Transfer
Hydrogenation
hexene
oxidase
is
decreases
conversion
[240]. Hydrogen-transfer achieved
with
solution
at 13OOC.
were
Methyl
the products.
of ammonium tative
yield
from methanol
Ru-phosphine
complexes formate,
If the reaction
acetate, according
to diphenyl-acetylene as catalysts trans-stilbene
was carried
hexamethylenetetramine to the following
was
in toluene and bibenzyl
out in the presence
was
formed
in quanti-
equation:
+ 3 PhCH2CH2Ph 3 PhC2Ph + 6 MeOH + 4 MeCCXXG14-
+ 6 H20 + 4MeCOSH
The formation result
of trapping
of methanol
of hexamethylenetetramine of formaldehyde
dehydrogenation
[241].
formed
was obviously as the primary
the product
443
b)
Hydrogenation Various
of C=O bonds
p-benzoquinones
to the corresponding lyst
in very
by iPrOH phenone
and 1,4-naphthoquinones
hydroquinones
good yields
C2421.
and dehydrogenation is catalyzed
suitable
by iPrOH with
Transfer
by Cp2ZrH2
The method
of primary
as cata-
of ketones
by benzaldehyde
at 130°C.
reduced
Zr(OH)20
hydrogenation
of alcohols
for the dehydrogenation
were
or benzo-
is especially
alcohols
to aldehydes
[243]. Alkyl using from
aryl ketones
iPrOH
hydrogenated
[244].
were
as H donor tuted
hydrogenation
and
[Rh(NBD)L2]+
The rate
increased
nation
synthesized
with
Optical
by iPrOH
yield
was
with
was
investi-
electron-donating
prop-
2,2'-bipyridines
in the transfer
in the presence
15% in the best
iPrOH
(L = p-substi-
of iPrONa
The new chiral as ligands
achieved
and ketones
as catalysts
increasing
[245].
and used
of acetophenone
as catalyst.
up to 75% were
in the presence
of the substituents
(83) were
yields
of aldehydes complexes
triphenylphosphines)
gated.
alcohols
and an -in situ Rh catalyst formed methionine sulfoxide, and KOH. Reac-
low but optical
Transfer
to benzylic
source
[Rh(l,5-hexadiene)C112,
tion rates
erty
were
as hydrogen
hydroge-
of [Rh(COD)C112
case
[2461.
(S)-EtMeCH
-
,-pF= (S)-PhMeCH
-
83 Asymmetric is catalyzed DIOP,
prophos
vated
by first
especially
hydrogen
(27), and chiraphos. treating
optical
(58%) was achieved [247].
When
achieved
[248].
dppp)
References p. 5 I4
from iPrOH
depend
have
catalytic
on activation
time.
catalyst
to be acti-
activity
and
Highest
0.~.
and acetophenone
in situ from Ir(COD)(acac) and the -P(men)2Ph and P(nmen)Ph2 proved to be active transfer
reaction
was used,
The complexes used
The catalysts KOH;
ketones
diphosphines
formed
acetophenone
were
to prochiral
of the chiral
an Ir/prophos
in the hydrogen
ketones.
dppe,
with
P(men)Ph2,
catalysts
them with
yield
The complexes
phosphines
transfer
by Rh and Ir complexes
optical
HIr(COD)L2
as catalysts
from
iPrOH
yields
(L = PPh3,
for the transfer
to prochiral
up to 42% were AsPh3;
L2 =
hydrogenation
444 of cyclohexanone like KOH were
c)
using
iPrOH,
not necessary
Hydrogenolysis
EtOH or MeOH
as H-donors.
for catalytic
by Hydrogen
activity
Cocatalysts
12491.
Transfer
See [2291.
11. Reduction a)
without
Transition
Metal
The binuclear lene
(85) which
rhodium
hydride
reactions
formation
(84) hydrogenates
shows
CIDNP
which
of the metal-centered
is the active
Ph2P-
Hydrogen
Hydrides
This
to styrene.
the reversible
Molecular
hydrogenating
agent
biradical
85
84 Low Valent
Transition
Unsaturated
the saturated substrates -OH group
Metal
dicarboxylic
to give
CP2Ti(CO)2
Ti(II1)
carboxylic
proved
PPh2
1 1 H ARh(CO)2 (CO)Rh* 1 I’H Ph2P,,PPh2
1 ,H, 1 (CO)Rh -Rh(CO) 1 ‘H’ i Ph2Pv PPh2
b)
by
isomer
12501.
Ph2P -
PPh2
phenylacety-
was explained
that
Complexes (e.g. maleic
acids
carboxylato
acid.
complexes
Experiments
the hydrogen
acid)
react
with
(86) containing
with deuterium-labeled
source
is the carboxylic
acid
[2511.
2Cp2Ti(CO)2
H\
+ HOOC ,c=c\
/H
COOH
0
-
Cp2Ti(
0 )C-CH2-CH2-C((
)TiCp2
0
0 86
Reduction p-hydroxy
ketones
to the carbonyl of reduction of ketones
of
c(,p -epoxy
group
probably [252].
ketones
in good yields. but
(e.g. 87) with
Stereochemistry
is lost at the
resembles
a.-position.
that of dissolving
SmI2 yields
is retained
p
The mechanism
metal
reductions
445 0 0
0 -
87
Functionalized vinyloxiranes like (88) have been found to undergo facile reductive epoxide ring opening with SmI2 in THF in the presence of a proton source to provide (E)-allylic alcohols (89). The reactions take place already at -9OOC and yields above 70% can be achieved in most cases [253].
R=COOEt,
CN, COMe
R 88
89
Several a-ketocarboxylic
acids and u -dicarbonyl compounds
were reduced by TiC13 to the corresponding a -hydroxycarboxylic acids and a -hydroxyketones, respectively [2541. Tricyclic epoxides like (90) were successfully deoxygenated to the corresponding olefins (91) in a one-step procedure using 2 equivalents of WC16 in refluxing THF [255].
OAc
-
OAc
The bifunctional complex [Co(salen)Na(THF)] promotes the reductive coupling of methyl pyruvate (92) to dimethyl dimethyltartrate (93) and of p-tolylcarbodiimide
(94) to tetra-E-tolyl-
oxalamide (95); the reductant is transformed into Co(salen) [2561.
References
p. 5 14
446
TH3
p -
2 MeCOCOOMe
MeOOC-C-C-COOMe AH bH
92
/-\ u-
.N=C=N
CH3eN=C-NHeCH3 CH3 CH3oN=!-NH+H3 95
94 Reduction
of substituted
gave pyrroles, PhCH=CHN02
could
ing oximes
mined
be reduced
Fe3(C0)12 good
c)
ArCH2CR=NOH
by CrC12
The biphasic
and HBF4
yields
in aqueous
with
reduced
in benzene
aqueous
by
12581. The 4was deter-
[Fe(CN)6!
of benzylic
afforded
Tic13 Thus
to the correspond-
15-17"s yields
of bromamine-T reduction
with
divinylamines.
THF to 3,4_diphenylpyrrole
were
ArCH=CRN02
of the reduction
[2591.
nitrostyrenes
and in some cases
oximes,
j2571. Arylnitroalkenes
kinetics
g3
thiols
desulfurized
with
products
in
[260].
Inorganic
Reductants
in the Presence
of Transition
Metal
Complexes The epoxide (97) by WC16
(96) was deoxygenated
+ BuLi
in refluxing
to the corresponding
THF with
98% yield
alkene
[261].
Me$o&oAc Me&&OAc
96 The Fe-S
cluster
the reduction nBuLi
formed
used
instead
(98) acts as an electron
of S-phenyl
and PhLi
ucts
97
thiobenzoate
to give benzil
from the
and benzoin
substrates
of the cluster,
transfer
and phenyl along
with
and the reductants.
practically
agent
benzoate
only these
coupling If FeCl
in
with prodwas
3 coupling prod-
447
ucts were formed [262].
PhS.
PhS’
98
The activity of the complex reducing agent obtained from tBuOH, NaH and Ni acetate could be significantly increased for the reduction of olefinic double bonds by the addition of Me3SiCl [263]. The reagent prepared from tBuOH, NaH, PPh3, and Ni acetate in an etheral solvent was found to be very effective for the reductive coupling of heteroaromatic halides (99, R' and R" = = H, Me, MeO, C4H4). Chlorides or bromides were better than iodides which often led to significant amounts of reduced byproducts (100) [2641.
R’ /
I3
x
R" ‘N
100
99
Reduction of alkyl and aryl halides by iPrMgBr, KBH4 or LiA1H4 is catalyzed by Ti complexes. A catalyst system containing Cp2TiC12 and iPrMgBr was found to be the most effective 12651. The nitrogenase iron center model compound (Et4N)4tFe6Sg(SCH2CH20H)Cll was prepared and its catalytic activity for the reduction of acetylene to ethene by KBH4 determined [2661. Reduction of acetylenes to olefins was performed by NaBK4 in the presence of FeC12 and dihydrolipoamide
(101) or a similar dithiol as catalyst sys-
tems. Best results were obtained with a catalyst containing equimolar amounts of Fe(I1) and dithiol. Hydrogen transfer probably took place within an iron-dithiol-acetylene complex and NaBH4 served to regenerate the starting complex [267].
m(CH2)4coNH2
SH References p. 5 14
SH
101
448 The mechanism and assisted ined
(reduction
found
that
acted
Rh(OEP)Cl
tion of aryl of other
found
d
The analogous
aliphatic
mild
or
nitro
+ [B02]-
groups
in MeOH
for the reduc-
in the presence
system
the deuterated
cycle,
and NaBH4
reagent
If the Cu 2+/NaBD4
reductants
re-
by Rh(TPP)Cl
of the catalytic
[269]. Copper(I1)
akcohol
as a black
12683. Aerobic
2 R2CH-OH
of cinnamaldehyde,
exam-
it was
stoichiometry:
to be an efficient,
the deuterated
formed
in THF is catalyzed
is borane
or LiAlH4 cases
halides)
catalyst
is an intermediate
functionalities.
produced.
(or aluminide)
NaBH4
and tertiary
with NaBH4
In the three
or alkyl
to the following
hydride
the reduction
nished
with
reductant
was
boride
+ [BH~I- + O2
A rhodium the actual
alkenes
as a heterogeneous
according
2 R2C=0
performed
investigated.
of nitriles,
of ketones
solution
was
the cobalt
precipitate duction
of reductions
by CoC12
was used
alcohol
for
(102) was
Ni2+/[BD4]- and Co2+/[BD4]-fur-
(103) under
such conditions
[270].
D /
phwCHo
102
CHDOH
.b Ph
103 D Diisobutylaluminium compounds
to saturated
has now been from MeLi tivity
found
unsaturated
(105)
Reduction
support
reduces compounds
that the addition
reagent.
carbonyl
by Pd(PPh3)4 propenes
carbonyl
and CuI) dramatically
of this
compounds
hydride
if
of MeCu
increases
The new reducing
compounds
ti,p -unsaturated
[104] to
HMPA
(prepared
the activity system p,u
carbonyl
is present.
It
in situ -and selec-
transforrnes doubly
-unsaturated
carbonyl
[271].
of
(E)-1,3-dichloropropene
and yields
only
(the Z and E isomers an allylpalladium
by Bu3SnH
two of the three
of 1-chloropropene-1).
complex
is catalyzed
possible
as intermediate
l-chloroThe results
[272]. Applying
449
the same method
for the reduction
l,l-dichlorobutadiene case
an oxidative
product
addition-
and a Pd(I1)
the catalytic acid media
species
cycle
of technetium
Reduction
by NH4Tc04.
is probably
Octene-1
was proposed of Pd(I1)
[273].
is catalyzed
as the only product.
p-elimination
Reduction
for the reaction.
of 1,1,1,4-tetrachlorobut-2-ene,
was observed
Tc(V)
is transformed
process
of methylene
blue
The catalytically
into octane
in MeOH
in the absence
of hypophosphite
place
Propargylic
acetates
by Sm12
in the presence
yielded
allenes
cases
in
form
is present. which
aqueous No hydroappar-
[275].
(106) were
of Pd(PPh3)4
exclusively:
of set-acetates
formed
by SnC12 active
containing
genation
as the H donor
completes
[274].
if KH2P02
takes
pathway
by Bu3SnH
or Rh(PPh3)3C1
serves
to the
as the probable
to Pd(0)
KOH and Ru(PPh3)3C12
ently
In this
leading
reduced
to allenes
as catalyst.
allene-selectivity
and from primary
acetates
and alkynes
tert-Acetates
was decreased mainly
alkynes
in were
[276].
OAc R--z--;-R”
I
-
Rj-.=(R’+ R-&q H’
‘R’
’I
R
106
See also
d)
12251.
Reduction
via Silylation
The homogeneous none monosilyl in refluxing
ethers benzene
reductive (107) was
found
[277!.
+ HSiR3
References p. 5 14
silylation
-
of quinones
to be catalyzed
to hydroquiby
X-&'Ph3)3Cl
450 d ,p -Unsaturated duced
ketones
at the olefinic
comprised
double
of Pd(PPh3)4,
-unsaturated
Ph2SiH2
carboxylic
the same conditions
and aldehydes
bond using and
Several
and aminophosphine-phosphinites the asymmetric complexes.
the product
nyl ethanol. and
Highest
chiral
(CL-naphthyl)PhSiH?
very
of
d ,p -
sluggish
tested
under (108:
as ligands
catalyzed
of the catalyst
re-
system
aminophosphinites
of acetophenone
and measuring
o.y.
selectively
The reduction
was
(109) were
hydrosilylation
Enantioselectivity
hydrolyzing
ZnC12.
acid derivatives
[2781.
were
a three-component
in
by Rh
was determined
the optical
purity
(43%) was obta ined with
after
of
CL-phe-
the ligand
(110)
12791. H
n/ Ph2PO
n/
NH
Ph2 PO
NPPh2 PPh2
108 Reductive Tic14
cleavage
+ Et3SiH.
the acetal reduction
The reaction
(111) could
‘* Alkyl
aryl
of
(-)-norphos
group
chemoselective:
with
for example, 112) without
[280].
in the presence
could
prochiral
[R~(NBD)c~]~
be
to undergo
of Rh(I)-phosphine
used
ketoximes
amines
hydrosilylacatalysts.
on hydrolysis
for the reduction
and -in situ catalyst systems phosphine like (-)-DIOP or
inductions
cat? -
and
of oximes
and a chiral
(115), optical
+ Ph2SiH2
shown
(114) yielded
t2811.
ioH
was performed
into the ether
(113) were
silylamines
Using
is highly
be transformed
ketoximes
accordinly this method
composed
to ethers
COOEt
Ph2SiH2
The resulting
amines.
of acetals
of the ester
tion with
110
109
up to 36% were
achieved
to
451 e)
Organic Reductants in the Presence of Transition Metals The use of 80% aqueous formic acid for enantioselective
transfer hydrogenation of N-acyl dehydroaminoacids using Rh(I) complexes of the ligands norphos (115), prophos (27), DIOP, and (116) was described. Addition of HCOONa increased the optical induction which in some cases exceeded the values obtainable with H2 [282]. H PPh2
‘NMe2
*z
t-Y
4
&_
PPh2
PPh2
(- ) - norphos
115 ;
116
The reduction of phenylglyoxalate
Me
(-)-
BPPFA
(117) to give methyl mande-
late by the NADH model compounds (118) or (119) is catalyzed by Lewis acids. Using chiral europium
p-diketonates
(shift reagents)
as Lewis acids optical yields up to 55% were achieved [2831.
PhCOCOOMe
-
PhC?HCOOMe dH
117
COOMe
CONH2
Me H
CH2F’h 118
119
The epoxides (120) were transformed into the hydroxy alkenoates (121) by stereospecific hydrogenolysis with ammonium formate catalyzed by Pd(O)-phosphine complexes. Yields were around 80% [2841.
Me
120
Referencesp. 514
R
R’
H
Et
Me
121
452 1,2-Dienes
(123) were
sis of alkynyl
carbonates
by Pd2L3.CHC13
+ PBu3
the dienes
were
prepared
by the selective
(122) with
ammonium
(L = dibenzylideneacetone)
reduced
to alkanes
hydrogenoly-
formate
catalyzed
at 30°C. At 65OC
[2851.
OCOOMe RA
* or OCOOMe
&-
R’
123
122 The hydrogenating system
(AS 1985,
Pd on carbon. reduction
activity
ref.
This new combined
of nitro
groups
(olefins,
ketones
(124),
an analog
of rubredoxin
anilines
nitro
conditions
complex
The ion pair chloride
catalyst
was
formed
shown
could
and after
again
transformed chlorides
sites,
to N-aryl
functional
[286].
Complex
catalyzes
the reduc-
hydroxylamines
addition
and
acetates
used
could
olefins
active
system,
salt could
species
be reduced
by using
to 1-methylnaphthalene
be
[2881.
water-soluble catalysts
took place
in the reduction with
of
by aqueous
crown-functionalized
as liqands
The
by addition
ammonium
and phase-transfer The reaction
from poly-
and acid chlorides.
of the quaternary
system.
In a similar
methylnaphthalene
olefins
transfer
in the form of NaRhC14
as chemical
(125) were
[2871.
the hydrogen
into the catalytically and ally1
two-phase
[2891.
phosphines
in situ
to acetylenes,
to the corresponding complexes
tane-water phase
of many
halides)
of
the selective
from RhC13. 3H20 and methyltrioctylannnonium
to catalyze
be recovered
Ally1
phine
active
compounds
(124) is formed
methylhydrosiloxane
HCOONa
and aromatic
by the addition
enabled
by o-xylene- cl,c(-dithiol. The reduction can also be by using FeC12 and Et4NC1 as catalyst since under such
achieved
NaC104
be increased reagent
in the presence
groups
tion of aromatic
of the HCOOH/Et3N/Ru(PPh3)3C12
274) could
formate
Pd phos in a hep-
in the aqueous triarylof l-chlorosalts,
cata-
453 lyzed
In this case the reaction
by Pd complexes.
in the organic
phase
was taking
[290].
n=l,Z
125;
Reductive halides
(hydroqenolysis)
dehaloqenation
was achieved
hydrosiloxane
or sodium
formate
Unsaturated
functional
olefins,
and ketones
were
[2911.
Phenol
as catalyst
by Pd(PPh3)$
solvent.
tions
place
as hydrogen groups
could
be selectively
aryl triflates
Et3N
of Pd(OAc)2
in the presence
these
functional
groups
and olefins
were
to tolerate
in MeCN/Me2S0 aldehydes, reaction
deoxygenated
(126) with
formic
and a tertiary
Unsaturated
found
donor
like nitro,
found to tolerate
of the corresponding
of organic
and polymethyl-
(X) like nitro,
by reduction acid and
aromatic
ketones,
the reaction
condi-
phosphine.
esters,
conditions
well
12921.
126
f)
Electroreduction
and Photoreduction
Electrochemical formed
with
electrode
reduction
a (Bu4N)3[Mo2Fe6S8(SPh)91-modified
in water
Hg electrode.
or with
Ammonia,
ry amines
were
was far more
cystine
formed.
a significant
The system efficient
catalytic
and improved
non-functionalized
the same complex
hydrazine,
electrode showed
of HOCH2CH2N3
current
aliphatic
In the case of secondary
References p. 5 I4
was per-
glassy-carbon in MeOH/THF
with
N2, and the corresponding based
[294]. Functionalized
were
and with
or tertiary
Co(TPP-OMe-E)
on the electroreduction
efficiency halides
a prima-
on the glassy-carbon
[293]. Heat-treated
effect
ced in DMF or N-methylpyrrolidone
and MeN3
electrochemically Ni(bpy)Br2
halides,alkanes
of or redu-
as Catalyst. and alkenes
454 were
the main
into dimeric
Water-soluble used
to catalyze
light
ic activity
cyaninato)
polymer-supported
to be a better (MV2+)
complexes
to MV'+
in methanol. [298].
IV.
Oxidation
1.
Catalytic with
cyclohexane
system
showed
catalyt-
for the reduction
Ru(bpy)<+
ions
the photoreduction yields
of Hydrocarbons
by ozone-air
with
84-89%
and. Cr(V1)
using
decrease
(Lu, Er, Y, of methylvioin the stated
or Hydrocarbon
of alkanes
in the presence
were
Groups
out with oxygen
.
5 as catalyst
superoxide.
for hydroperoxides
oxygen
Ketones
as 49% were
in the presence
of Ni(st)2
and carbonyl
of carboxylic
acid
b)
of Olefins
of Cr(C0)6
in the system
form of reduced
as high
salts of Co, Cr, and [2991. Oxidation
at low conversions.
present
was carried
yields
Oxidation
and polymetal was examined
selectivity
Fe30(0Ac)6py3
is probably
coulombic
in the product
[3001.
of
gave cycloCr(III), Hydroxylation
in CF3COOH
+ py as
and a cathode
as reduc-
in this electrochemical were
the main
attained resulted compounds
products
[301,3021. in hiqh
selectivi-
and. a hiqher
or Alkynes
of 2-alkenyl
and 4-alkenyl-di-tert-butylphenols
by Co(salpr)
leads
of oxygen
the side chain
corresponding
carbonyl
(129),
selectively
to the incorporation
and thus to the formation
compounds
oxygen
content
[303].
Oxidation
into
and
Oxidation
(127) promoted
derivative
of
[297!. Biscphthalo-
lanthanoid(II1)
quantum
of paraffins
The active
tant.
ties
Relative
of individual
of cycloalkanes solvent
were
by visible
of Alkanes
The effect
Cr(IV),
viologen
02
Mn on oxidation
hexanone
mainly
phthalocyanines
photocatalyst
of several
Oxidation
Oxidation
a)
metal
of methyl
than
Gd, Eu, Sm, Nd, and La) catalyze logen
transformed
The Ru(II)-tris(1,4,5,8_tetraazophenanthrene)
[2961.
order
were
The Ni and Cu complexes
solution.
proved
methylviologen
halides
[2951.
the photoreduction
in aqueous
dication
primary
products; products
(128). In the case
is incorporated
both
of the
of the alkynyl
into the side chain
455 (product
130) and into the ortho
position
(product
131)
[304].
R
OH
127a
128a OH
OH
R
A0
127b
128b
tl 129 The cleavage bony1
compounds
Rh(PPh3)3C1. solution
The reaction
diene-1,4-dione Some Ph3P0
molecule
of olefins
is catalyzed
at the double by several
requires
[305]. Homocooxyqenation
that both
occurs
is also 0 atoms
formed.
air oxidation
(LL = dppe
of olefins.
terminal
Formation
olefins
concentrations
labeling
containing
alkenes
yielded
of O2 in
give cyclooctaas catalyst. showed
to the same diene bidentate
were used
of ketones
linear
mainly
to
experiments
are transferred
Rh complexes
e.g.
of RhC1(PPh3)302
or Ph2P(CH2)2SPh)
reaction in the case of terminal and branched
enhanced
Isotopic
in the complex
bond by O2 to give car-
Rh complexes,
of COD by O2
in the presence
[306]. Cationic
[R~(LL)~BF~
Referencesp. 5 14
131
130
liqands
to catalyze
the
was the predominant while
products
cycloolefins of allylic
Some epoxidation
oxidation. neous
oxidation
of octene-1
or Pd(I1)
species
octene-1.
Oxidation
of oxidizable mediates
isotopically
became
Hydrido
catalytic
complexes
[3071.
catalyzed
labeled only
were
Homoge-
by Rh(II1) 02 and
in the presence
supposed
as inter-
13081. of cyclopentene
solvent
by PdCl2
ethylacetamide)2].
formed
from a palladium
is probably
[3091.
of ethene
to vinyl
ketone
acetate
is catalyzed by
is produced
by one mole
in turn,
which
derives
as a catalyst
than the analogous
02; the may be
its H from
[Pd,,l(phen)801(PF6)60
active
in
[PdC12(N,N-di-
hydroperoxide
which,
cluster
to be more
effectively,
a palladium
hydride
The giant
and found
to cyclopentanone
or, more
One mole
species
pared
using
of olefin
active
ethanol
in all cases
by 02 or tBuOOH
was studied
alcohols.
Oxidation ethanol
occurred
was pre-
in the oxidation iPdgG1(phen)60!(OAC)180
[3101. Aldehydes of 1-alkenes
tem
the major
air using
and a tertiary
cuc12, cuc12
were with
or the tertiary
of alkene
alcohol
were
vatives
(133) in about were
not formed
that comprises
omitted
(PdC12,
(132) yielded
vatives
of the catalytic
No aldehydes
alcohol.
[311]. Wacker-oxidation
stereomers
products
a catalyst
40% yield.
CuCl, the
were
terminal
no chloride of chloride,
134
sys-
The isomeric
benzoyl
phenylacetyl
derideri-
mF’h 133
oxidation
of 3,3-dimethyl-4-pentenoates
under
Wacker-conditions
in the reaction
the corresponding
COOR
either
from the catalyst
corresponding
-
was achieved
was present
when
02, H20) of the two dia-
132 Selective
formed
13121.
&p, (134, R = Me,Et)
oxidation (MeCN)2WClNO2,
methyl
mixture.
ketones
j-ooR
AcO
in AcOH
if
In the presence
were
obtained
[313].
451 Olefins were oxidized to ketones by 02, PdC12, CuC12, and water using a cyclodextrin to transfer the organic molecules into the aqueous phase. The relative reactivity of cyclodextrins as phase transfer agents for the oxidation of 1-decene to 2-decanone was
[314]. Based on the unexpectedly high trans P'a'Y influence of the OH- ligand it was proposed that the rate-deter-
mining step of the Wacker-oxidation of ethene is the attack of H20 on PdC12(0H)(C2H4)-
[3151.
See also [364].
c)
Spoxidation of Olefins The reaction of singlet oxygen with alkenes in the presence
of Ti alkoxides was employed to prepare epoxy alcohols. If diethyl tartrate was used as chiral auxiliary the reaction could be performed with high enantioselectivity; e.g. in the case of (135) the (S)-enantiomer of (136) was formed in 72% o.y. [3161.
02 /TPP/hv OH
Ti(OBd)4/(+)-DET 135
136
Olefins could be epoxidized by O2 in the presence of Mn(TPP)Cl, 1-Me-imidazole (as axial base), and benzoic anhydride if electrolytic reduction was applied. Faradaic efficiency of the system was 56% which is high if compared to analogous systems using chemical reductants [3171. The catalytic system composed of the NADH analogue (137), flavin mononucleotide
(138), N-methyl-
imidazole, Mn(tetraphenylporphyrintetrasulfonate) anhydride
and benzoic
(or benzoic acid) was found to be a highly efficient
catalyst for the epoxidation of olefins with 02. Any systemlacking one of the components did not show activity: if Mn was replaced by Fe the activity was much lower. Significantly, the structure of each component is very close to that of the native P-450 system [3181.
References p. 5 14
458
CONH2
Me
Air
oxidation
furnished
0
137
of norbornene
as the main
product
138
catalyzed
by
(MeCN)2PdCl(N0)2
exo-epoxynorbornene
concentrations
and a tetrahydrofuran
concentrations
[319].
(139) at low
derivative
(140) at high
&--4P” +q$-y H 139 See also
d)
[307,
3461.
Oxidation
of Aromatics
Aromatic
hydrocarbons
artificial
P-450
were
type catalytic
N-methylimidazole, creased
colloidal
the overall
as catalyst
was determined
for the formation The formation
coal during studied. tion
The results
of alkyl
groups
system
number with
hydroxylated
consisting
of HCl in-
conditions
were
concerning
sample
opti-
[321]. acids
of Ru04 as catalyst
provided information the coal
of oxida-
of Mn(st)2
(C2-C6) monocarboxylic
in the presence
by the
(TPP)MnCl,
02 in the presence
and the reaction
within
of
[320]. The kinetics
of the dihydroperoxide
of volatile
oxidation
effectively
Pt, 02 and H2. Addition
turnover
tion of m-diisopropylbenzene
mized
140
from
was
the distribu-
[322].
460 The reduction the catalytic CO(OAC)~
of CO(OAC)~
oxidation
+ NaBr
by xylene
of xylene
catalyst
with
[334]. The complex
and chloro-substituted
alkylaromatic
NMR.
that
It could
oxidation decreasing
be shown
of these
compounds
of the complexes
studied
as part
formation
compounds
the catalytic
alkylaromatic
stability
was
O2 in the presence
with
[335].
between
has been
activity
CoBr2
studied
of CoBr2
O2 increases
Oxidation
of
of a
by
in the with
of ethvl-
461
HyH20
-- 02
Me
Me 141
142 --,CH
-CHO
\o’
A heterogeneous-homogeneous the oxidation
of anthracene
of Ag ketenide See also
a) Oxidation
of Alcohols
of O-containing
The heteropolyacids anchored
H3[PMo120401
of iPrOH
the Ze-reduced
conditions
at 30°C.
[345].
chloride
by O2
was
diols
[343].
suggested
were
of ally1
investigated found
below
involves
and reoxidation
under
of
of cyclohexanol complexes each
in sub-
the reaction
by O2 catalyzed
in the pH range and above
as cata-
in aceto-
which
first order
alcohol
O2
and used
and Ru(III)-EDTA
EtOH was not oxidized
with
Photocatalytic
[344]. The kinetics
by Ru(II1)
was acrolein
were
by (Bu~N)~(W~~O~~)
was
The reactions
were
Groups
H4[SiMo120401,
by the decatungstate
Oxidation
kinetics
of oxidation 2.5
species
and catalyst.
Ru(II1)
A mechanism
by O2 catalyzed
studied
reaction
of primary
of the substrate
oxidation
Functional
H6[C0W~204~],
by O2 catalyzed
was studied.
oxidation
strate
for
by 02 in the presence
to poly(4-vinylpyridine)
for the oxidation
oxidation
was
to anthraquinone
[304].
Oxidation
nitrile
was demonstrated
[3421.
2. Catalytic
lysts
143
mechanism
by
l-3. Different
pH 2.0. The product
at pH 1.5 and glycidaldehyde
(143) at pH
[346]. The reactivity
plexes
toward
of coordinated
H abstraction
from Co to 02. Low electron the same time associated References
p. 5 14
dioxygen
is controlled transfer
with
in CoL4(B)(02)
by electron
enhances
low affinity
reactivity
toward
com-
transfer but is at
02. These
two
462 effects
determine
the oxidation
the catalytic
of secondary
activity
alcohols
of 2-ethylhexanol
by O2 in the presence
mainly
by the reactions
determined
and the 2-ethylhexanal ethanol
in the presence
is the abstraction
of PPh3.
PPh3
P(OMe)3
of racemic were
substrate
used
1-phenylethanol
used
were
is oxidized
(144) were
as axial
oxidized
kinetic
resolution
tivity
was obtained
as catalysts
rates
The giant
Pd cluster
subsequently
(144~)
Oxidation catalyzed gands
of alcohols
by Cu(1)
complexes
and counteranions.
the order
4,4'-Me2bpy
able product
was
Cu(I1)
complex
phatic
alcohols
found
R,
;
R = OMe,
144c
R = H,
;
Effectivity
with
to aldehydes
to partial enantioselec-
H R’=H R’
q
Me
the oxida-
the aldehydes
are
[3511. or ketones using
with
O2 and
different
of the complexes
li-
decreased
in
and Cl- > Br- > I-. No detect-
imidazole
(145) was shown
PPh3 or of the
catalyzes
investigated
> bpy > phen
R’=
144 b ;
to aldehydes was
Co(I1)
for the oxi-
Best
or ketones:
into esters
which
[350].
Pd561phen60(OAc)180
by O2 to aldehydes
transformed
leading
alcohol.
144a
tion of alcohols
by H202 to OPPh3
The two enantiomers
at different
PPh3 and
step
[3491. The chiral
by O2 to acetophenone;
ligands.
of the unconverted with
is catalyzed
The rate-determining
of the catalyst
dation
of a -phenyl-
atom by the 02 coordinated
leads
complexes
is
the substrate
{and H202 as byproduct)
to co. In a side reaction
Schiff-base
with
13481. Oxidation
of the a -hydrogen
to the deactivation
for
of Co 2-ethylhexanoate
of Co(II1)
intermediate
by O2 to acetophenone
by Co(salen)
of such complexes
13471. The rate of oxidation
or py as ligand
to catalyze
[3521.
the oxidation
by 02 in the presence
of KOH
The
of ali[3531.
463 b)
Oxidation
of Phenols
The reaction
of Mo(3,5-tBu2-catecholato)3
3,5-di-tBu-1,2-benzoquinone reaction
constitutes
the oxidation
According tures,
complexes
complexes
(dissolved
oxygen process
probably
atoms were
proceeds
was
of (146) by O2 in
(149)
in situ from FeC13
studied.
The reaction
complex,
and incorporation
and
mix-
of pyri-
semiquinonato-Fe(I1)
formed
by ring opening.
(148),
a series
of the reaction
via
complex
of a catecholate
accompanied
through
O2 in the presence
[3551. Oxygenation
intermediates
(147),
spectra
with
in THF) and the ligands
by the formation
This
describing
[354].
of an Fe(III)-bpy-py
to form peroxide
02 gives
scheme
O2 to benzoquinone
of catechols
as intermediates
the presence
ceeded
with
MO complexes
to EXR and Moessbauer
the oxidation
dineiron(III)
one step of the reaction
of catechol
of well-characterized
with
and Mo202(3,5-tBu2-catecholato)4.
Final
reaction
pro-
with
O2
of one of the products
of this
[356].
0
152
Oxidation various
Co, and Mn with lysts.
of
catalyst
(150) with systems.
the multidentate
The Cu,Co,
and Mn complexes
of the corresponding
References p. 5 I4
O2 was
studied
Thus the binuclear
benzoquinone
ligand
in the presence complexes
(151) were
promoted but with
of
of Fe,Cu,
tested
the selective
as cataformation
the iron complex
also
464 the
lactone
quinone
in a nonaqueous
[358] and catalyst
phase
[CuCl(p~)]~ the byproduct
-Co(acac)2-02
complex
the Cu catalyst could
formation
base
was
peroxo
of phenols
complexes
was
of di-,
studied
to be water
and
of a catechol-
could
be observed
step.
and the
of the o-quinone. The was proposed as the rate-
complex
to quinones
investigated
tri-,
in different
of Co(salen)
solvents
in the case of o-cresol
by Co-Schiff 13601. Oxi-
to p-quinones
and other
No reaction
as catalysts.
used
by O2 catalyzed
and tetramethylphenols
in the presence
base complexes conditions
found
step.
Oxidation
dation
was
for the preparation
of a dinuclear
-determining
Co(acac!2
to be the rate-determininq
no ring cleavage
be used
using
In the case of the Co
The decomposition
was assumed
to the corresponding
investigated
of the oxidation
be detected.
reaction
has been
[359] as catalysts.
no H202 could
With
[357]. Oxidation
(152) was formed
Co!II)
was observed [361].
Thymol
by O2 Schiff
under
the
(153),
carvacrol
(154) and o- and m-cresol were oxidized with O2 and Co as catalyst to the corresponding p-benzoquinones with high
salen yields
13621.
Me
Me
3 Q
OH
OH iPr
iPr
153 The Co(II) catalysts
Schiff
154 base
corresponding
better
their
stability
(155) were
of 2,6_dimethylphenol
p-benzoquinone.
than that of the analogous complexes
complexes
for the oxidation
Although
their
oxidative
to be usefu
by O2 to the
activity
ethylenediamine-derived against
found
was lower
Schiff
decomposition
[363]. Me Me
Me Me
t-t R=H,OMe
base was
465 Oxidation with
of isoeugenol
O2 and the Co(II)
the reaction
was about
as byproduct
[364].
(156) to vanillin
complex
(157) was performed
(159) as catalyst.
Selectivity
75% and dehydroisoeugenol
(158) was
of
formed
156 158
The direct lyzed
by Cu(1)
air oxidation and Cu(II)
some of the catalyst ating
ligands
enhance
for oxidation hydroquinone the latter complexes and
tested
were
exhibited
nuclear catechol
were more
N-ethylated
followed
p. 5 I4
active
complexes
membranes
Cu(I1)
containing
Mononuclear
of the Cu(I1)
Catalytic
and aqueous
to of
base of
(150)
pyrrolic complexes
of (150) and diof 4-methylcomplex
of
in the oxidation
of
oxidation
of alginate-Cu(I1)
a Michaelis-Menten
Schiff
in the oxidation
activity
[3671.
in the presence
preparation
for the air oxidation
poly(4-vinylpyridine)
was studied
from Na-alginate
one-pot
reactivity.
used
of benzoquinone
for the oxidation
The catalytic
hydroquinone
References
active
[366].
was performed
tions
In general,
Binucle-
The Cu catalysts
and dinuclear
as catalysts
complexes
partially
formation.
is cata-
solvents:
> 90% selectivity.
a convenient
the highest
found to be more
aprotic
the hydrogenation
[365]. Mononuclear were
to p-benzoquinone
in polar
achieve
o-quinone
affording
4-methylcatechol.
residue
systems
also catalyse thus
of phenol
complexes
solutions
type kinetics
of hydroquincne
membranes
prepared
of CuC12.
Oxida-
[3681. Oxidation
of
(160) to
lyzed
has been
were
(162, polyphenylene
complexes
active,
a DMAP:Cu
ratio
by 02 and cata-
the most
that
both mono-
active
species
mixture
product
95%
increased
the yield
(DMAP)
and dinuclear
beinq
Cu(DMAP)4Cl(OH).
of 4:1, Cl- as the counter-ion
OH- to the reaction (162) above
oxide)
of 4-(N,N-dimethylamino)pyridine
It was concluded
studied.
complexes Using
(161) and
by Cu(I1)
and addinq
of the desired
[369].
Me
Me
162
160
cl
Oxidation
of Aldehydes
Oxidation with
of propionaldehyde
Co acetate
found
as catalyst
to be 1.5 order
catalyst
and Ketones
[3701.
into perpropionic
in acetone
in aldehyde
The redox
+ EtOAc
and 0.5 order
properties
presence
d)
was
in O2 and
with their like
role
isobutyric
in cataacid or
of cyclohexanone
with O2 in the
of Cr(II1)
or Co(I1)
naphthenate
successively
1,2-cyclohexanedione, acid anhydride
[330, 331,
Miscellaneous The catalytic
the oxidation
13731.
gave
E-caprolactone,
2-hyadipic
[372].
3321.
Oxidations activity
of oxalic
rate was observed HCl
each
Oxidation
and adipic
See also
as solvent
[371j.
droxycyclohexanone, acid,
by 02
of l2-molybdophosphates
were studied in connection MxH3-xPMo12040 lyzing the oxidation of organic compounds methacrolein
acid
of Fe
2+
phthalocyanine
acid was studied.
derivatives
The highest
in the case of Fe-phthalocyanine
oxidation
treated
with
for
467 The kinetics
of oxidation
by RuC13. nH20 or different plexes
has been
the stability
these
An inverse
studied.
and catalytic
The rate of oxidation latter
of ascorbic
relationship
activity
which
acid com-
was
of the Ru(II1)
did not depend
catalysts
acid by 02 catalyzed
Ru(III)-aminopolycarboxylic
found between chelates
on 02 concentration
act as oxidase
models
[3741.
with
in this
reaction
[3751. Oxidation
of sodium
oxalate
with
phthalocyanine.2py)adduct
as catalyst
of a histamine-containing
polymer
dation
of ascorbic
Michaelis-Menten ascorbic
saturation
hibit
oscillatory
regime
were
specified
liquid-phase even
small
oxidation copper
amine
See also
13711.
Catalytic
The amount
sharply
oxygenolysis
inhibitor
Organic
shown
on the addition
by Fe, Co, Cu or Mn phthalocyanines. inhibits
by
Compounds of
by O2 in the presence of Na2C03
Addition
[3821.
The
(165) is cataof py or imid-
+
COMa NH2
NHCHO
164
of
Diisooctyl-
[3831.
COMa
p. 5 I4
in the
in the presence
(163) to (164) and
lyzed
Rcfcrcnces
to ex-
peroxide-initiated
in the oxidation
azole
163
of
of tetra-
13811.
to N-methylsuccinimide
the reaction
a
of CU(OAC)~
as inhibitors.
byproducts
of 3-methylindole
was
was studied
of N-containing
increased
showed
by 02 is decreased
The dicumyl
amines
activity
in the oxi-
of the oscillatory
The activity
esters
aromatic
a(Co
Oxidation
of the Cu complex
[380].
of polymeric
N-methylpyrrolidone of KMn04
3791.
was an efficient
Oxidation
[377].
of Me isobutyrate
of water
different
The catalyst
The conditions
of pentaerythritol
using
diphenyl
3.
[378,
oxidation amounts
complex
tetraazacyclohexadecine
character.
using
[3761. The catalytic
behavior
acid by O2 in the presence
benzo[l,5,9,13][b,f,j,n]
studied
latex-Cu(II)
acid was examined.
type
02 was
165
468 of Et3N by O2 to Et2NH
The oxidation by a Ru(III)-EDTA reaction
was
Anilines derivatives carbon too
studied
in MeOH
and MeCHO
in situ. --
is catalyzed
The kinetics
of the
13841. by O2 and Co(salen)
at reflux
temperature.
isocyanates
or urethanes
of aromatic
ketone
as catalyst
to azo
In the presence and ureas
of
are formed
3861.
Oxygenation Co(salen) benzoate
prepared
are oxidized
monoxide,
[385,
complex
as catalyst derivatives
of methylimidazole
in MeOH
hydrazones
resulted
and aromatic as additive
ketones
diazo
(166) using
in the formation [387].In
compounds
of methyl
the presence
(167) were
formed
[388].
//
X
X
X
yOMe
+
!I
0
X = H,Cl, NO2
166
R = H,Me,Ph,COPh N2 167
The binuclear catalyst diamine inact ive
Co(II)-Schiff
for the oxidation with
(168) was used
as
of N,N,N',N' ,-tetramethyl-p-phenylene-
Oz. The analogous
[389].
base complex
mononuclear
complex
was practically
469
Hydrazobenzene Co(salen)
was oxidized
by 02 into azobenzene
(169) or its bis(3-methoxy,)
A mechanism proposed
involving
a complex
derivative
of substrate,
using
(170) as catalyst..
catalyst,
and 02 was
[390].
n
The Cu(I1)
complexes
phenylpyrazole
of 1-methyl-3,5_diphenylpyrazole
could
be used
as catalysts
of 1-methyl-3,5_diphenylpyrazoline Oxidation in MeCN (171)
of o-phenylene solution
diamine
yielded
or 3,5-di-
for the dehydrogenation
in the presence with
the protonated
of 02
[3911.
air in the presence
of Cu
2,3_diaminophenazine
2+
cation
[3921.
Oxidation catalyzed
of N-benzylidine-o-phenylenediamines in pyridine furnished different
by CuCl
ing on the substituents group.
In most
obtained imidazoles coupling
of the amino
p. 5 I4
ring
caused
the E-methoxy
groups
cyclization derivative
to the diazo
O2
depend-
in the benzylidene
2,2'-diaryl-l,l'-bibenzimidazoles
substitution
(174) and with
[3931.
References
cases
but ortho
of the benzene
(172) with products
compound
(173) were to 2-arylbenzonly
oxidative
(175) was
found
470
R,R‘=H
172 QJ~=CH-p-@
175 R=H R’ = OMQ
II
Indolines [CuCl(py)&as selective
(176) were catalyst
oxidized
in CH2C12
to indoles
(177) with
O2 using
solution.
The reaction
was rather
(up to 92%) and no ring cleavage
was observed
[3941.
i-R2
-
H
H 177
176 Autoxidation cu(11).
Reaction
ternary
complex
mediate
which
the products
of diaminouracils products between
reacts [395].
(178) is strongly
are H202 and imines
diaminouracil,
with
an ionic
Cu(I1)
two-electron
catalyzed
(179). Probably
by a
and O2 is the intermechanism
to give
471
178
See also
4.
[402].
Catalytic
Oxidation
The Fe(I1) catalyst
of P- or S- Containing
complex
Fe(OPPh3)4(13)2
for the oxidation
p -peroxo
complex
[Ru(EDTA)(PPh3)1202
The rate-determining
complex
Ru=O(EDTA)(PPh3) in the oxidation
function
of L. Best yields
as axial
ligand
garded
and
7 bar in MeOH
Oxidation
Co(I1)
hexylamine
overall [402].
studied
as a
process
is strongly
of Ce(IV)
at 25OC
silica
via
complexes
with
rate was controlled
coordinated
by the proceeds
reaction
is catalyzed
by Co(I1)
a bond with
of O2 and CU(OAC)~.~H~O
species
re-
useful
were
found
and yields with
probably
to of
cyclo-
as catalyst
(180) were
thiolate
by the reoxidation
py. The
was
of 2-mercaptobenzthiazole
active
were
Oxidation
of bis(salicylal-o-phenylenediamine) active [4011. The kinetics, selectivity
in the presence
with
[3991. Aut-
accelerated
salts.
and is a synthetically
condensation
wzre excel-
synthesized)
in the catalytic
to amorphous
The catalytically
hexylamine
(TPP)Co(No2)(L)
to sulfoxides
give N-cyclohexylbenzothiazole-2-sulphenamide gated.
of
L = 4-cyanopyridine
complex
the oxidative
as an inter-
The all-trans-RuX2(SR2)2
separately
of EtSH to Et2S2
anchored
be the most
the
of the ruthenyl
by O2 was
with
of thioethers
solution.
amount
13 bar O2 at 100°C
[4001.
to Ph3PO
to sulfoxides
of a catalytic
complexes
identified
activity
achieved
13961.
as catalyst
(X = Cl,Br,SnC13,SCN)
(which were
of sulfides
addition
were
RuX2(Me2S0)4
as key-intermediates
oxidation
under
of Ph3P
for the oxidation
complexes
(Me2SO)2
was
to act as a
[398].
The complexes
O2 at 105OC
found
Compounds
by O2 in MeCN
step is the formation
[397]. Catalytic
complexes
lent catalysts
was
to Ph3PO
of PPh3 by O2 and Ru(III)-EDTA
In the oxidation
mediate.
of Ph3P
Organic
to
investi-
Cu-cyclo-
ligands of Cu(I)
and the to Cu(II)
4’12
+ II2
H2N
+
02
-
a&S-NH0 + H20
180
The kinetics Mn(I1)
of oxidation
iminodiacetate
of cysteine
immobilized
presence
of iron phosphate
See also
[306].
5.
a)
Catalytic
Oxidation
Inorganic
Oxidants
02 in the presence
complexes
of Organic
14041 was
Compounds
of
[4031, and in the studied.
with
Organic
or
General The high valent
were prepared active
acceptor
H202
Mn complexes
by oxidizing
species
are able to transfer
mation
of active
Ru(PPh3)3C12 tate.
[406].
of organic
systems
substrates
Oxidation Oxidation
tions
compounds
gave
by
in dry aceto-
for peroxidases,
catalases
was obtained
and
for the forfrom RuC13
and
and phenyliodosoace-
for the oxidation
or Hydrocarbon with
anthraquinone
groups
could
(181) were
(182) were proposed
tBuOOH
of a vide
variety
Groups
in the presence
in 97-100%
be oxidized
in dichloromethane
chromate
and FeC13
[405!.
compounds
[407].
of anthracene
methylene
by tBuOOH
the cyclic
be used
of Hydrocarbons
acetylacetonate Benzylic
may
system
organic
N-oxide
These
to any good oxygen
(metal 0x0 species)
N-methylmorpholine
(TMPjMn(OjBr
or NaOBr.
(TMPjMnX/NaOCl
evidence
intermediates
with
These
as models
Spectral
and
NaOCl
of different
of Fe(MeCN)4(C104)2
were'investigated
monooxygenases
with
one 0 atom
in the
and dehydrogenation
in the presence
nitrile
(TMPjMn(OjC1
(TMP)MnCl
and act as catalysts
Oxygenation
b)
with
on Silochrome
solution
yield
into carbonyl if small
used as catalyst. as intermediates
of Mo(V1)
at 40°C
[4081.
func-
amounts
of
tert-Butylperoxy [4091.
473
181
Oxidation been
of styrene
investigated
catalyst
with
182
to phenylacetaldehyde
by two cytochrome
NaOCl
as oxidant
P-450
and Fe(PFP)Cl
kis(pentafluorophenyl)porphyrinato]. is a primary
product
styrene
oxide
ketones
were
Mn(TDCPP)Cl MeCN
[410].
as the catalyst
as solvent. [411].
has been
demonstrated
porphyrins
Shape
selectivity group
with
also
er degree. those
various
for some
chain mechanism phenol
ionol
Oxidation under
and
was
of alkanes
hindered
metallogood regio-
at the least
hindered
were
oxideand
could
studied.
be completely
to or better
than
of
(183) as catalyst
With
t-butyl
of peroxide
iron
to a less-
[412]. Oxidation
complex
cyclohexenyl
The formation which
was
although
comparable
enzymes
the Mn(II1)
as cocatalyst
The corresponding
selectivity,
cyclohexene peroxide
involved
inhibited
as
were
a free radical by the hindered
[413].
of benzene
air has been
It was concluded,
References D. 5 14
tBuOOH,
cyclohexene
the two products.
agent
as oxidant
as catalyst.
good primary
w -hydroxylase
with
and py or imidazole substrate
into a!.cohols and
of imidazo1.e and in
sterically
for hydroxylation
acetate
showed
olefins
of
of the catalyst
iodosobenzene
The regioselectivities
found
the aldehyde
for the hydroxylation
very
With
[PFP = tetra-
that
[5,10,15,20-tetrakis(2',4',6'-triphenylphenyl)
porphyrinato)-Mn(II1) complexes
degradation
by using
was observed
of alkanes
has
Mn(TPP)Cl
from isomerization
in the presence
selectivity
as catalysts.
+ C6F510
H202 as an oxidizing
No significant
observed
methyl
High conversions by using
systems:
It was shown
and does not result
obtained
and epoxide
model
to phenol
investigated that oxygen
and benzoquinone
using
isotopic
is included
with
tracer
from both
H202+Fe
techniques.
sources
into
2+
474
the reaction
products
the process (H202, NaI04,
PhIO,
Fe(III)-bleomycin under
anaerobic
explained
and that
i413a;. Oxidation
and cumene
leads
deactivation
complex
the oxidation catalyst
with
was encapsulated
form as catalyst
Two types
benzene.
in the oxidation increased
lyst was
cumene
acetamides
selectivity
in competition
by NaI04
Cycloolefins and
RuC13.xH20
were
obtained
were
in MeCN/Ac20
were
oxidized
as catalyst with
oxidized
to the corresponding
two-phase
system
ternary
ammonium
was hydride kinetics
in which
with
NaOCl
salts
as oxidant
as catalysts.
abstraction
by phenyliodosoacetate zero order substrate
with
but zero order
acids
acids
respect
to both
oxidant
of C2-C4
olefins
with
[419].
NaOCl
results of glutaric
derivatives
were
in > 90% yield
and both
Initial
were
with
Best
case the yield
oxidation
or Pb(OAcj4
2
in
of Fe(C104j3
system.
Ru salts
in a
and qua-
step of the reaction
by Ru04 from the methyl
of the Ru(III)-catalyzed
at position
as cata-
benzene
carboxylic
and
of Fe(S04j2
in the presence
[420]. Methyl-substituted
cyclohexane
cyclododecane
to dicarboxylic
cyclopentene
82%
by iodoso-
to the corresponding
in a two-phase
acid was
Iron and used
Oxida-
and catalyst oxidized
in
3 and 4 [4171.
in the presence
in substrate
Hydrocarbons
i4161.
of oxidation
at positions
acid by H202
and Fe
The best
were observed:
the extent
to that
No
zeolites
of alkanes
with
The
as catalysts
large pore
of shape
order
[418].
tested
p -0x0 dimer
inside
be
in the presence
hydroperoxide.
oxidized
respect
first
oxidant
14141.
mechanisms
[4151. Cobalt
were
for the oxidation
of n-octane
with
tion of crotonic
group
[4211. The
of phenylacetic
studied.
acid
The reaction
and first
order
was
in Ru and
[422].
Oxidation the presence
of Pd(OAcj2
tivity.
From
ethene
formed,
higher
products
was observed
of cyclohexene
was preferentially
and
could
of N-dodecyl-3,4_dihydroxybenzamide.
was an iron tetraataporphirin
is this
oxide
The results
investigated
and tetraazaporphines
phthalocyanine
cis-stilbene
oxidative
by ~202 was
during oxidants
in the presence
to trans-stilbene.
of the catalyst
phthalocyanines
regenerated
by different
hydroperoxide)
two parallel
of anisole
of the Fe(II1)
is in part
to benzaldehyde,
conditions
by assuming
hydroxylation
H202
of cis-stilbene
yields
mainly
olefins
[4231. Methylbenzenes
to quinones
with
aqueous
glycol
ethylene
yield
H202
HI04
glycol
in AcOH
acetates
glycol
solution
with
diacetate
monoacetates
selec-
is being
as principal
and methylnaphthalenes in AcOH
high
and in
in the presence
were
oxidized
of a Pd(II)-
475 sulfonated
polystyrene
1,4-napthoquinones ities were
rather
tion and reused The Cu(I1) in refluxing
(184)-(186)
ucts
[426].
could
2+ S208 oxidation
or Cu(I1)
and the dimeric
oxidation
salts
An allylic
to
selectiv-
be recovered
of 9-methylanthracene
and aqueous
MeCN.
Side-chain
compound
(187) were
by filtra-
gave
radical
of butenes
with
prod-
the main
prod-
tBu peroxyacetate
3-acetoxybut-1-ene
and a Cu(II1)
[427]. Polynuclear
was studied
oxidation
186
185
Allylic
Selectivities
[424, 4251.
184
mediates
at ZO-80°C.
50 to 70% but 1,4-benzoquinone
low. The catalyst
MeCN/AcOH
ucts
type resin
were
and trans-acetoxybut-2-ene.
complex
aromatic
and Cu(I)
were
supposed
hydrocarbons
were
as interoxidized
by
'- with catalytic amounts of Ce(IV) and Ag+ in a two-phase '2'8 system using (BU~N)(HSO~) as phase-transfer catalyst. Naphthalene could way
be transformed
with
70% yield
in this
[428].
See also
c)
into o-naphthoquinone
[308, 332,
-oxidation
Asymmetric
440, 469, 5081.
of Olefins
epoxidation
of ally1
alcohol
using
tBu00H/Ti(OPri)4/diisopropyltartrate
system
into a practically
The strategy
References
p. 5 I4
useful
procedure.
the
has now been developed employed
consists
in the -in situ derivation its decomposition
of the very
alcohols
could
only
employing
catalytic
ester
tBuOOH
amounts
(6-13 mole
present
pyl tartarate and at least
(5-10 mole
%j if 3A or 4A molecular
with
alcohol
giving
(188) was
both enantiomers
88% optical
yield
were
to asymmetric
i+)- or
:-)-diisopro75-77X
chemical
-
189
epoxidation
of Ti(OPrij4
propyloxiranemethanol [432]. A practical
izeolites)
(189j with
188
Asymmetric
out with
14311.
OH
presence
of allylic
carried
subjected
of
thus pre-
%) and tartrate
sieves
and Ti(OPr i\,4, using
tBuOOH
epoxide
epoxidation
be successfully
of Ti(OPri)4
!4301. Allylic
epoxidation
reactive
14291. Asymmetric
venting
of E-2-hexen-l-01
and diethyl-
2R,3R
in 80% yield
and 96,8%
and efficient
method
with
tBuOOH
-tartrate
gave
in the
!2S,3S)-3-
enantiomeric
purity
for the preparation
of both
enantiomers
of the erythro-epoxy secondary alcohol (191) from the allylic alcohol (190), based on the Sharpless kinetic reso-
racemic lution
process
epoxidation tartrate. into
has been developed.
of
(190) with
The unreacted
tBuOOH,
First,
Ti(OPri)4,
enantiomer
(191b) by epoxidation
with
(191a) was prepared
of
tBuOOH
and
!+j-diisopropyl-
(190) was then and VO(acac)2
transformed 14331.
SW3 nBu
MQ
/ + OH 190
nB”aMe
nB”q_ AH 191 a
by
OH 191 b
477
Asymmetric oxidation of methyl p-tolyl sulfide to the corresponding sulfoxide by tBuOOH in the presence of Ti(OPri)4, diethyl tartrate, and water and asymmetric oxidation of (E)-geraniol (192) with the classical Sharpless reagent was investigated using (+)-diethyl tartrate of varying enantiomeric purity. It was found that the correlation between the enantiomeric purity of the chiral auxiliary and the optical yield of the asymmetric synthesis strongly departs from linearity [4341.
r- -
r-OH
192
Asymmetric epoxidation of the divinylcarbinol (193) with tBuOOH and Ti(OPri)4 in the presence of L(+)-diethyl tartrate gave the epoxides (194) or (195) depending on the workup procedure [435]. Epoxidation of (193) according to the above method in the presence of 4A molecular sieve gave the epoxide (194) in 60% yield [436].
n
194
OH
I
193
I
Ho+ I.*
H
References p. 5 14
195
479
Cyclohexene and different methylcyclohexenes were oxidized with PhIO or m-MeC6H410 in the presence of VO(acac)2. Epoxides and allylic oxidation products were formed: the results were in accord with a free radical mechanism [440]. The dienes (202; R = Et,CoOMe) were epoxidized by tBuOOH in the presence of VO(acac)2 with high regio- and diastereoselectivity to epoxides (203) [4411. PhCOO
OH
The stepwise epoxidation of COD with tBuOOH in the presence of MO complexes was studied. The second epoxidation was at least five times slower than the first one [4421. Epoxidation of refined soybean oil using Mo02(acac)2 as catalyst [4431 and that of sardine oil using Mo(C0)6 as catalyst [4441, in both cases with cumene hydroperoxide, was studied. Empirical kinetic equations were determined in order to optimize operating variables. Epoxidation of cyclohexene by tBuOOH catalyzed by MO complexes was investigated by IR and UV spectroscopy. The results suggested on initial rapid reaction of the catalyst with tBuOOH to give a MO peroxo complex which then epoxidized the alkene [4451. Molybdenum peroxide immobilized on a chelating polymer was used as catalyst for the epoxidation of olefins with tBuOOH. Isolated product yields ranged between 38-89% and the catalyst could be reused several times, preferably after reactivation by H202 [446]. Simple monoolefins were effectively epoxidized with H202 and a catalytic amount of a quaternary phosphonium or ammonium pertungstate at 40-SOOC. The catalyst could be prepared also -in situ by the addition of tungstic acid and Ph3PCH2Ph+C1- to 30% H202 14471. The scope of the tungstic acid catalyzed epoxidation of olefinic alcohols by H202 has been examined. Epoxidation occurred with complete retention of configuration for both eis and trans alkenes and no isomerisation or cleavage of the olefinic bond was observed 14481. This epoxidation afforded in the case of allylic alcohols the same diastereoisomer as the VO(acac)2 + tBuOOH system. Epoxidation of homoallylic alcohols appeared to be much less stereoselective [4491. The transition metal substituted heteropolytungstates (Bu~N)~[H(M)PW~~O~~~ (M = Mn, Co) are remarkably effective
References p. 5 14
480 catalysts oxygen
for the epoxidation Product
donors.
stabilities favorably
of olefins
selectivities
using
! 3,YO%),
PhlO or C6F510 reaction
rates,
as and
(10000 eyuiv, of C F IO per equiv. of catalyst: compare 6 5 with those for metalloporphyrins and related systems
14501. The kinetics has been is the
formation
either
reacts
reaction
these
terminal !4521.
of
olefins
was
species
[453!.
complex
attributed
used
which
NaOCl
in a two-phase was necessary
NaOCl
Ph groups
of
changed
had a synergistic
effect.
:a bywroduct
a H atom onto
the mechanism synthesized
for the epoxidation system.
of
system
Methanol
(204j was
(CH2C12 + H20)
.4511.
in the presence
transfers
changes
+
in a biphasic
to phenylacetaldehyde
and thereby
agent
and KHS05
with
!
for the epoxidation
was investigated.
The new porphyrin as a catalyst
in an equilibrium
on the ueriphcral
as catalysts
and styrene
of styrenej
limiting step -t which
j (TPP)Mn=O'
1 (TPPjMn-O-MniTPP:
LiOCl
of alkenes
as catalyst
of the reaction
latter
manganese
NaOCl,
and Mn'TPP'OAc
the rate
comnlex
complexes
suitable
with
by NaOCl
that
or is transformed dimer
!TPP)Mn!III)
compounds
the epoxidation
tion
the olefin
Epoxidation
kinetics
epoxidation be shown
of the oxomanganese
with
MniTPP-Me-&OAc
This
It could
into the unreactive
Substitution makes
of olefin
studied.
the
of
an 0x0
of the reacand its Mn!III
of olefins
with
No phase-transfer
14543.
204
The Mn(II1) be effective benzene.
complexes
catalysts
[Mncsubstituted
for the epoxidation
Electron-withdrawing
groups
salenjl+
were
of olefins
enhanced
found
with
the activity
to
iodosylof the
481 catalyst; the relative reactivity of olefins depended only slightly on the structure of the substrate. Epoxidation was stereospecific and only minor competition from allylic oxidation was observed [455]. The Mn(II1) complexes Mn(L)Cl, Mn(L')Cl and Mn(L)(N8) (H2L = 205a, H2L' = 205b) have been found to catalyze the epoxidation of alkenes with PhIO. These new catalysts show high chemoselectivity: cyclohexene oxide was the only product in the oxidation of cyclohexene [456].
205a
R=H
205 b
R =Cl
Epoxidation of cyclohexene with PhIO was investigated under identical conditions using different metalloporphyrins
(PMX) as
catalysts. Using TPP complexes,Mn and Fe were found to be the most selective metals (M), with Fe as metal meso-tetramesitylporphyrin was the best porphyrin ligand (P) and among (TPP)FeX catalysts C104 was most effective as axial ligand (X) [4571. Six different alkenes were epoxidized with E-cyano-N,N-dimethylaniline
using
(TPP)FeCl, (TDCPP)FeCl, or (TDMPP)FeCl as catalyst. Best yields (80-100%) were obtained with (TDMPP)FeCl. The rate determining step of the catalytic reaction was the transfer of oxygen from the oxidant onto the iron complex [458]. Along with the epoxidation of alkanes with PhIO catalyzed by Fe tetraarylporphyrin chloride complexes, three important side reactions were observed: formation of PhI02, destruction of the porphyrin ring, and N-alkylation of the porphyrin ligand. The latter reaction was only observed in the case of monosubstituted olefins not hindered in the vicinity of the double bond. The same alkenes act as suicide substrates of cytochrome P 450 [459]. Using Fe(TDCPP)Cl as catalyst for the epoxidation of olefins with C6F510 it was observed that N-alkylation of the porphyrine ligand takes place. Depending on olefin structure 100 to 10000 moles of epoxide were formed per mole of N-alkylated catalyst. This side reaction significantly decreased the act.ivity
References p. 5 14
482 of the catalyst Oxidation
but did not lead to complete
of 2,4,6-tri-tert-butylphenol
-butylphenol
radical
and epoxidation
no-N,N-dimethylaniline catalyst
has been
the formation species
[461].
roperoxybenzoic which
reacts
tuted
styrenes
0 +. copy
acid
with
systems tected
were
developed
than
TPP
The ratio
different catalyst
of exo-
substituted
electron
radical
give a carbocation sylxylene
skeletal (207a)
206,
by C6F510
and
two-phase
Ar=
by UV spectros(CH2C12/H20)
of olefins.
The pro-
stable
and active
!Fe=O)+
!4641.
product
obtained
followed
Epoxidation
as catalyst
formed
from the and using
complexes
as
that the mecha-
to the iron(W)
by radical
collapse
of cis-cyclooctene gave the cis-epoxide
also took place
!465;.
suggest
from the alkene
If trans-cyclooctene
(207b) were
j 3‘
9
or iodosylxylene
The results
transfer
cation
rearrangement
nism was proposed
suecies
the Hammett
[ (tetraarylporphinato)Fe(III)l
and Fe(TPP)Cl
exclusively.
with
to give more
to endo-epoxy
of norbornene
involves
be
!463].
has been determined.
porphyrin
cally
found
radical
was observed
for the epoxidation
(206) were
could
with m-chlo-
In the case of substi-
correlates
+ NaOCl
Ar
epoxidation
porphyrin
to
radical
or Fe(TMP)OH
an oxo-Fe(IV)
Iron(IIL)-porphyrin
leading
Ti: -cation
to give epoxides.
of an intermediate
Ar
nism
of Fe(TMP)Cl
by Q-cyaas
(TDCPP!FeCl
for the oxidations
the rate of reaction
porphyrins
catalyst
gives
olefins
[460?.
olefins
of
and equilibria
porphyrin
rate constants
The formation [462].
Rates
of the iron(oxo
Oxidation
of different
in the presence
investigated.
and minimal
determined
N-oxide
deactivation
to the 2,4,6-tri-tert-
with
to iode
practi-
was epoxidized
in this way
and the carbonyl
compounds
as byproducts.
A carbocationic
mecha-
OH0
- c&J +
Lz
207 a
of cholestery ,1 acetate
Epoxidation systems
as Mo(C0)6
reoselective showed
high
concluded radical
while
+ tBuOOH a radical
that epoxidation process
[466].
(LH~ = 208) catalyzes though
with
low yields
by nonradica 1 reagent
or Fe(C104)3 reagent
with
the
+ H202 was highly
system
Based
p -stereoselectivity.
207 b
like Fe(acac)3
on this
(TPP)FeCl
+ ~EuCOH
observation
+ PhIO
The binuclear
iron complex
the epoxidation
of olefins
(l-3%)
a -ste-
it was
system
is a
(Me4N)[Fe2L(Opc)21 with
H202,
al-
[467].
,CH2COOH
208
The synthetic and their of cis-stilbene (209b-d)
Fe(II1)
analogues complexes
and trans-stilbene was highly were used
iron complex
(209) of bleomycin used
with
suppressed
suggesting
in these
cases
as catalysts H202.
been prepared
for the epoxidation
The epoxidation
of trans-
if the tBu-substituted a highly
derivatives
crow&ad environment
of the
[468].
R'
R2
aH
H
H
bH
Bu
R
209
Referencesp. 514
have
c OMe
Bu
d Cl
Bu
t t t
OBllt OBu OBu
t t
484 The Ru(IV) stilbene
0x0 complex
in acetonitrile
be performed
also
as catalyst
[(bpy)2(py)RuOl
solution
in a catalytic
and NaOCl
case,
due to the oxidative
fission
-porphyrin
iOEP)Os(PBu3)Br
complexes
as catalysts PhIO.
Turnover
the case
numbers
around
of cyclohexene
oxidant,
system
and
100 were
agent.
In
are formed
!469:. The Os(III)-
(TPP)OsiPBu3)Br
of cyclohexene
were used
and styrene
obtained.
was cyclohexanone.
can 2+
with benzyl-
of benzaldehyde
of the C=C bond
for the epoxidation
The oxidation
as phase-transfer
amounts
styrene
! (trpy)(py:lRu(OH2)1
in a two-phase
chloride
significant
however,
in high yield. way by using
as oxidant
dimethyltetradecylamonium this
,2+ epoxidizes
with
The byproduct
If tBuOOH
was used
in as
complex
cyclohexanol was the only product 1470;. The Os(VI) dioxo 2+ reacts with PPh3 to form OPPh3 and the 0s:III) [Os(LH2)02]
complex
Os(L)(PPh3)Cl
the epoxidation mediate
was observed
Several lysts
during
dinuclear
analogous be
See also
solution.
These
mononuclear achieved
with
Th'is latter PhIO.
epoxidation
copper
for the epoxidation
nitrile
could
(LH2 = 210).
of cyclohexene
of olefins
complexes.
have been tested
with
to be much With
4141.
inter-
as cata-
iodosylbenzene
in aceto-
more
than
complex
in the case of cyclohexene
[410, 413,
catalyzes
colored
[471].
complexes
proved
complex
A highly
effective
(211) 70% yield as substrate
14721.
485
d)
Oxidation
of O-containing
Functional
Di- and trimethylphenols quinones metal were
by H202
metal
polyvanadatotungstate actually
oxidized
and the vanadate by HN03 occurs nedione only
and alkali
were
oxidized
as catalysts.
by [VO(O,),i+
2 routes.
to the corresponding
polyvanadatomolybdate
hydrates
[473]. Oxidation
via
Groups
which
was
formed
of cyclohexanol
One of these,
from H202
to adipic
involving
as intermediate,gives a significant 5+ of V 14741.
or alkali
The phenols
yield
acid
1,2-cyclohexa-
of adipic
acid
in the presence Primary
sponding
and secondary
carbonyl
Na2M004. 2H20 as catalyst Oxidation
alcohols
compounds
of furfural,
with
under
could
dilute
be oxidized
H202 using
phase-transfer
thymine,
to the corre-
Na2W04.2H20
conditions
and EtOH by H202 was
or
[4751.
studied
with
MO or W compounds with
as catalysts [4761. Aqueous H202 in conjunction 23amounts of W04 and PO4 , under acidic conditions,
catalytic
provides
a synthetically
tive cleavage
use of tungstate yields
alone
alcohols
olefinic
alcohols
Phenol
Detailed tions
oxidized
oxida-
acids.
decrease
The
of the
was oxidized
by aqueous
ions to yield
investigations
were
between
1.5:1
catalytic
oxidation
than that
of Fe3+
(EDTA)Fe(III)
radical,
the peracid
[4811.
References D. 5 I4
of differ-
and hydroquinone. 3+ Fe . Optimized condi-
with
14791.
The efficiency
by H202
in aqueous
transfer
(212) were
in methanol
and a peroxidic identified
of Fe2'
in the
solution
is higher
from percarboxylic
for the reactive
formaldehyde and
in the presence
catechol
investigated
reagent
[478].
of 84% and catechol:hydroquinone
of phenol
has been
too
ratio of
yields
[4801. Oxygen
(212) as a trapping Phenoxyl
- 2:l
H202
(molar
for the oxidation
alcohols
performed
in good yields
with Mn(OAc)2
was suitable
and of secondary
metal
to aldehydes
in combination
gave dihydroxybenzene
ratios
for the selective to carboxylic
to a significant
The new method
ent transition
from
were
lead tetraacetate
1 : 0.1-0.5).
to
leads
procedure 1,2-diols
[477].
Primary using
useful
of water-soluble
solvent,
iron-oxo
intermediate.
component
as organic
acids using
formed
products
486
CH3 212
:I
CH3 4
CH3
6H
Oxidation catalyzed
of benzoin
by
to benzil
ing peptides
or bulky
of this reaction
thiolates
is shown
by E-benzoquinone
complexes
!Fe4S4(SR)412-
containing
as RS groups.
below
could
be
cysteine-contain-
The catalytic
cycle
14821:
Ph-C -C -Ph d
8
Ph-Cl-i-C-Ph bti
Sodium conversion
bromate
of alcohols
Ce or Ru compounds nary ammonium reaction.
into carbonyl
oxidation
of primary alcohols
of lactic
The effect
oxidized
Ru(PPh3)3C12
and lactic
acid
by N-methylmorpholine
were determined
acid,
and qlycolic
RCHO + H20
to carboxylic G===
[( 7j6-E-cymene)20s2(CI -OH)31(PF6).
for the
in the presence
has been
studied.
of a 1:l
[484 1. Secondary
alcohols
in the presence
in 80% yield
acid by IO, catalyzed
the
of the Ru(III!-catalyzed
N-oxide
for the oxidation
of aldehydes
ing the equation
was selective
of
Quater-
accelerated
by the formation
in DMF to give ketones
stans
Oxidation
was explained
Ru(II1)
reaction.
into aldehydes
14831. The kinetics
for the
in the presence
catalysts
oxidation
alcohols
oxidant
two-phase
acid by peroxodiphosphate
of Ru(II1)
between
compounds
as phase-transfer
The cerium-catalyzed
of secondary
were
found to be an effective
in an organic-water
salts
transformation
complex
was
II
1485'.
of mandelic by RufIII) acids
with
acid,
lactic
chloride water
RCOOH + H2 is catalyzed Raising
of
Rate con-
the temperature
14861.
accordby to 60°C
487 and adding
a base
(Na2C03)
turnover
numbers
glycolic
acid and lactic
is first order could
the rate of the reaction;
be oxidized
with
achieved
[487].
acid by chloramine-T
in oxidant
(214) in 73% yield. necessary
enhances
of up to 100 were
[488].
NaI04
The furan
and 0s04
Isolation
catalyzed
of
by Os(VII
ring of khellin
(213)
in THF to give the aldehyde
of the intermediate
diol was not
[489]. OMe
OMe
0
214
213
Hydroxylation
of the cis-enoate
(216) in 87% yield.
the tetrabenzoate in the presence
0
OMe
6Me
diol
Oxidation
After
(217) the furan of Ru02 to give
owMe
(215) with
transforming ring could
(218)
Os04
afforded
this compound be degraded
the
into by NaI04
[4901.
o*ph
_
216
215
R = PhCOO Me0
Me0
Palladium ary alcohols presence
salts
of K2C03.
References p. 5 I4
catalyze
into esters
the oxidation
and ketones,
Allylic
alcohols
of primary
respectively,
give addition
and second-
by Ccl4 products
in the with
488
halohydrin
structures which,
corresponding hols were chored
at higher
successfully
PdC12
as oxidant useful
ketones
or homogeneous
of K2C03. of
using
as catalyst The method
alco-
polymer-an-
and bromobenzene
was especially into fi4,6 -dien-3-
(219’
A 5-sterols
into the
'491:. Steroidal
into ketones
Pd(PPh3)4
in the presence
(220)
are transformed
temperatures
transformed
for the conversion
-ones
however,
14921.
HO 220
219 A first-order of formic See also
e)
acid
The PhNHNH2
of amines
of indigo
dyes,
catalyzed
murexide,
by EPR spectroscopy
by H202/TiC13
by VO(acac)2 for example
was
PhNMe2
applied
during
14941.
Oxidation
studied.
Oxidative
gave
PhNHMe
polymer-supported
and azo-
o-dianisidine mechanism
were proposed catalysts
by
oxidized
Tc(VI1)
was proposed
14971. prepared
for this
from
or Na noly!D-glutamate) of L-DOPA
H202 or p-benzoquinone _
in acid media
by
or poly-
by H202
CH2=CH(CH2)3CH=CHCH2NEt2 14991.
into MeCO(CH2)3CH=CHCH2NEt2 by
and lumogallion
oxidation
amine
of
The oxidation
of ethylenediamine
and Na poly!L-glutamate)
tertiary
complexes
!496!.
lumomagneson,
complexes
for the stereoselective
selectively
H202 using
was studied
carmin,
Mechanisms
The unsaturated
of Na2PdC14
dyes with
with Mn(I1)
as catalysts.
[Re!tetpy)!OH)21+
was
Compounds
was observed
of different
The chiral
[498:.
Organic
triethylenetetramine
H202 was studied
were
!4931.
[495].
with
amines
for the oxidation
5781.
was observed:
Oxidation Mn(I1)
radical
by Cu(I1)
of phenylhydrazine
by PhIO2
dealkylation
573,
of N-containing
the oxidation
was determined
by S208*- catalyzed
[461, 569,
Oxidation
benzene
rate constant
is catalyzed
reaction
[5001.
in the uresence
The oxidation
of
by Cu!IT).
A
489
See also
f)
L419, 459,
Oxidation
of P- or S- Containing
The asymmetric sulfoxides
416, 5971.
oxidation
was achieved
of catalytic complexes
amounts
(221,222).
Organic
of sulfides
with
cumene
of optically Optical
into the corresponding
hydroperoxide
active
yields
Compounds
Schiff
ranged
in the presence base-oxovanadium@V)
between
20-40%
[5011.
R
O,i,O / - ’
OO/\ \;,
c&t,
-
_N/
&“&
lN-
y,? 221; R= H,OMe,OEt, It was Mo(IV)
transfer
that
the Mo(V1)
[224] reduces
in DMF
sulfoxides, ferase"
shown
complex
222;
tBu
solution.
N-oxides
system
complex
several
Thiols
and Ph3As0
R = H,Me
(223) oxidizes
organic
compounds
and PPh3 were oxidized were
reduced
by this
while
"0x0 trans-
[502].
+
Accordingly,
complexes
(223) and
of sulfoxides
R2SO+
Asymmetric
2
R’SH
oxidation
by thiols
and diethyltartrate high
as catalysts
+
R’SSR’
+
H20
(225; n = 2) with
gave the corresponding
and optical
for
[503]:
of dithiolanes
(226) with
chemical
(224) acted
RSR
-
Ti(OPri)4,
ReferencesD. 5 14
x0
224
223
the reduction
and the
by oxygen
yields.
tBuOOH,
sulfoxides
By contrast,
the
490
analogous
(225; n = 3) gave much
dithianes
lower
optical
yields
15041. 0 II
R\C,sl(CH2)n
R’/
R\C,sl
-
\S/
R’/
225
Asymmetric been
furnished
(227a) and
226
S-oxidation
investigated
system
using
of the chiral
different
predominantly
(227bj,
the trans
the two stereoisomers
from
N-R’
x Rs
R2
oxidants.
isomer
(227d)
227
from
type
of
(229) was
studied
Ti(OPri)4.
(228) with
The relative
on the Ti compound
in the case of
(227~) and a mixture
R2
R3
a
CH20H
CH2Ph
Me
Me
b
CH20H
CH2Ph
nPr
H
c
CXSle
MO
tBu
H
CR2Ph
Me
Me
active
hydroperoxides
and in the presence
of the cis and trans
composition
of these
strongly
HW,
NR’
-
R”R”
228 (racemic)
229
6 230 (four
of
depended
R
+ r-i X
of
of
isomers
[506].
S
of
R'
in the absence
(230) and the enantiomeric
The tBuOOI_I+ Ti(OPr')4
R
optically
yields
(227) has
[505].
dCKNe
Oxidation
thiazolidines
the cis sulfoxide
R d S
(CH2)n
\c/
enantiomers)
491
Thiophenol aniline
was oxidized
N-oxide
Optically
active
tion of chiral as catalyst.
to diphenyldisulfide
in the presence triols
of Fe(TPP)Cl
(232) could
allylic
be prepared
J3-hydroxysulfoxides
The diastereoselectivity
between
72-95%;
sulfone
it dropped
if the sulfoxide
J5071.
by the hydroxyla-
(231) by Me3N0
of the reaction
was previously
to 308, however
by N,N-dimethyl-
as catalyst
and 0~04
ranged
oxidized
to the
[508].
Me OH 232 Thioethers -transfer
were
catalysis
and Cu(OAc)2 See also
6.
Metal
Oxidation
were
by chromic electron
acid.
-5OOC
studied.
The data
atom abstraction
References p. 5 I4
releasing
substituents
that
the initial
favored
pathway
to
was extremely
toluenes
fluorochromate step involves
of eudesmol
an
J5llJ.
upon mixing
of substituted
by pyridinium
rate cinnamic
hydrocarbons
The reaction
is
to form
metallo-
Second-order
in Ccl4 was oxidized
[513J. Oxidation
bond
of substituted
oxidized
hydro-
hydrogen
reactions
a radical
and ketones.
of oxidation
aldehydes suggest
J5101.
substituents
of n-hexane
The kinetics
the corresponding
latter
Cr02(00CCF3)2,
alcohols
model
step allylic
for the oxidation
withdrawing
a solution
Hiqh Valent
to the double
In these
Electron
trifluoroacetate,
J5121.
then adds
as intermediates
determined
give predominantly rapid:
phase-
Groups
in the gas phase
In the first
products.
can be supposed
constants
ionic,
alkenes
processes.
and other
Compounds - -.-__~-_with
or Hydrocarbon
to form CrOH which
aldehydes
Chromyl
of Orqanic
of CrO+ with
oxidation
abstracted
acids
under
of Bu3(hexadecyl)P+
Complexes
of Hydrocarbons
Reactions
cycles
by NaI04
in the presence
[434, 6141.
StoichiometricOxidation
carbon
into sulfoxides
[5091.
Transition a)
oxidized conditions
(233) with
at to
has been hydrogen dipyridyl-
492
chromium
trioxide
gave
(234) and two isomeric
Me
ketones
Me
cn
CMe 20H
I t!j
[5141.
CMe20H
Me 233
Alkynes compounds
were
by
The role with
234
oxidized
of mercuric
the alkyne
in the presence
acetate
thus
Cc -dicarbonyl
to the corresponding
(HMPA)MoO(02)2
is probably
favoring
of mercuric
to form a
oxidative
attack
acetate.
Tt -complex
by the metalperoxi-
de 15151. The kinetics
of permanqanate
Cr,p -unsaturated buffered
carboxylate
to electronic These
important.
effects
results
to which
the MnOi
to yield
a metallacyclooxetane
tion
of solid
C=C bond
acid
to yield
THF solution. creased
ion undergoes
paraffin
the carboxylic
tadiene
with
KMn04
salts
of reaction
alkenes Mn02.
in CH2C12
This product
phonium polar
ions had
solution
is accompanied
derivatives
solvents
little
effect
has been
de-
by MnOq
in ben-
of dicyclopen-
It was shown
intermediate.
at the
in a dilute
substituents
Oxidation
cation
improved
cleaved
of quaternary
that
the rate
by the rate of decomposition
detectable
permanqanates
In the oxida-
in the presence
investigated.
is stabilized
of styrene
organic
15191.
the C=C bond
with KMn04
of ethylbenzene
size of the ammonium
by Bu3MeN'Mn0i
Oxidation
products
were
to be
according
of n-hexadecane
and bulky
Oxidation
was determined
increasing
main
by Bu4NOH
has been
spectrophotometrically with
as
with 15161.
[5171. Olefins
increased
[518].
zoic acid was catalyzed
ammonium
addition
appeared
mechanism
cycloaddition
by KMn04,
Conjugation
the yield
the accepted
in phosphate
to be not very
factors
intermediate
selectivity
aldehydes
found
but steric
support
of substituted
investigated
(pH 6.8). The rate was
solutions
sensitive
ion oxidation
ions were
of a
The rate
increased
!5201. Oxidation
by the
formation
by adsorption
of the alkane
by quaternary
ammonium
studied
such as acetone on the rates
in different the structures
of reaction:
of
of colloidal [521j.
and phos-
solvents.
In
of the cat-
significant
dif-
493
ferences
were
as CH2Cl2 (235) with
however,
in less polar
[522]. Oxidation
cetyltrimethylammonium
6 -1actones oxidative
found,
or toluene
(236) with cyclization
R
good yield.
organic
permanqanate One carbon
solvents
such
6 -hydroxyolefins
of y- and
leads atom
to y - and
is lost in this
[5231.
OH
‘C’ R,/ \
236 (CH~),,CH =CH2
235
The ethylenic
lactones
the dibenzobutanolides cyclic tate)
compounds
(237, R1-R6
(239)
(238) and
15251 were
= H,MeO,OCH20) oxidized
(240) by Ru(IV)
tetrakis(trifluoroace-
in situ from Ru02, trifluoroacetic -tris(trifluoroacetate), and BF30Et2 in CH2C12-
formed
acid,
R’ 238
References
P. 5 14
[5241 and
into the tetra-
Tl(II1)
494
OMe
OMQ
R =H,Ot'&
OMe
OMQ
240
239
Transformation was
investigated
nes,
of allylic
using
and acetates
opposite
perbenzoic
acid
osmylation
i526].
used
achieved
Optical
Hydroxylation
of olefins
to vicinal
in the nresence
up to 86% were
achieved
from L-tartaric
for this purpose.
Optical
yields
with
siloxa-
diols
by 0~04
of chiral
with diamine
acid
(241)
have also been
up to 90% were
(242) in the case of trans-stilbene
/a
sulfides,
in epoxidation
derived
example
by 0~04
with m-chloro a hyperconjuqative model for
enantioselectively yields
diols
diastereoselectiv-
diamines
15271.
Chiral
sulfones,
The observed
and did not support
be performed
diamines.
to those
into vicinal
silanes,
as substrates.
ities were
could
chiral
groups
achieved
for
15281.
NM42
242
241
NMe2
The indenopyrene by first sulting
treating diol with
(243) was transformed
it with
0s04
activated
into the quinone
in py and then
Mn02
oxidizing
!529]. 0
243
244
(244)
the re-
495
Oxidation
of E-xylene
the effect
4_Methylbenzaldehyde, acetate
were
probably
nium
selectivity
by bromine
and Co(II1)
reaction
transfer
is the
H atom abstraction
dation
of olefins
glycol
monoacetates. were
her.
found
intermediate
were
[533].
acidic
Several
intermediates
nism
involving
for this
15351.
one
with
solution
were
were oxidized
monoacetates
media an
organic
as
with
solvents and ver-
to acetaldehyde The nitrito the reaction
by spectros-
by PdC1(N02)(MeCN)2 ref.
was
radical
-pinene
during
identified
(AS 1985,
intermediate
and was high-
verbenol
studied.
complex
in
515). A mecha-
(245) was now proposed
[536].
245
References p. 5 I4
a
of ethene
was
allylic
involving
of
products
and
[5321.
a cation
and in different
of the process
the acetoxonium
olefins of tri-
in acidic
oxidation
into a nitrosyl
Olefins
[5311. Oxiacetates
olefins
mechanisms:
Oxidation
operate
system
monoacetates
complexes
oxidation
[534].
to glycol
reaction
plausible
gave allylic
and an other
ammo-
The regio-
in the Co-containing
from aromatic
solutions
Side-chain
that the two oxidants
of glycol
by Pd(I1)
in CH3C1
was transformed
solution
formed
The allylic
complex
AcOH
the yield
is
by Ce(IV)
in the oxidation
The liquid-phase
predominant
methods
in AcOH
by two different
by Pd(ONO)C1(MeCN)2
copic
[5301.
in the Ce-containing
to be more
products,
were
investigated.
benone
Brz
In the case of disubstituted
intermediate
in aqueous
PdC12 was
The reaction
investigated.
step while
seems
of xylenes
to proceed
organometallic
first
olefins
Both products Oxidation
suggests
by CO(OAC)~
the main
tetrasubstituted
has been
and
studied.
and 4-methylbenzyl
radicals
mechanisms:
system
acetates
alcohol products.
anion
acetate
of the reactions
different
electron
oxidation
has been
of 5-substituted-1,2,3_trimethylbenzenes
nitrate
with
acid by Co(III)-acetate
reaction
4-methylbenzyl
the organic
initiated
oxidation
in acetic
of Br2 and py on this
Oxidation aldehydes
of toluene
by
be catalyzed
by anionic
rate enhancements interaction See also b)
were
into the correspondinq
in a two-phase
reaction
surfactants like Me(CH2)llOS03Na. interpreted
in terms
The observed
of a micelle-substrate
of Olefins
The polymeric
yield
peroxo
titanium
found
derivatives
to epoxidize
Ti02tL: :HMPA:.H20
tetramethylethylene
with
15381. COOH
COOH
I
yN HOOC /U‘N
HOOC
‘I J3‘N
246 The novel red and used
247
vanadium(V)
alkylperoxy
for stoichiometric
showed
that
in agreement
with
process
step.
complexes
epoxidation
the olefin
the rate-determining
dation
benzcould
[334, 5641.
(L = 246 or 247) were
studies
system
:537 1.
Epoxidation
5-15%
derivatives
(NH4)2CeiN03)6
coordinates
The features
the general
(248) were prepa-
of olefins. to the metal
of these
characteristics
Kinetic prior
epoxidations
of the Halcon
to are
epoxi-
[539]. R
/ b -
248
0’
R =H,Me,CI,NO2
\ /
Epoxidation occured
of cis-2-butene-1
stereospecifically
4-diones
(249) by Mo05.H20.HMPA
to give the cis-epoxides
(250)[540!. R=Ph,Me,OMe
0
PhC
R
t
6
0
___c
ph-C
A 8
249
-R d
250
497
Stoichiometric (M = W,Mo) tungsten
complexes
complex
two peroxo geraniol
has been
was more
groups
react
gave
studied
in CH2C12
rates
(252) with
the epoxides
suggests
OH
at 40°C.
The
be shown that
the
[5411. Epoxidation
the same complexes
(253) and
does not involve
with M0(02)2(HMPA)
and it could
at different
in regioselectivity
and W complexes
of olefins
active
(251) and linalool
chloroethane change
epoxidation
(254), respectively.
that epoxidation
a coordinated
-
with
substrate
of
in diThis
these MO [5421.
OH
253
251
OH
OH
G\
0 252
254
Peroxomolybdenum ligands
were
found
complexes
to exhibit
(255, 256) containing
asymmetric
induction
chiral
in the epoxida-
tion of -trans-2-octene. Optical yields were about the same (highest value 11%) whether monodentate or bidentate chiral ligands were used
[543].
255,
L* = e.g.
256;
L* =
L” H20
O,i,O hyyd L* See also
References
p. 5 14
[526].
Q_CJ.
?” 40
CH3 CHC ‘NMQ2
498
Oxidation
Cl
of O-containing
Oxidation
of benzaldehyde
in HClO 4 was
V5'
first
order
indicated
found
by vanadium(V)
The kinetics
of oxidation
The kinetics acid media mic
acid
was
of butene-1,4-
dation
ied using groups
of oxidation
investigated
with
in the presence complex
acid and tartaric
in ayue-
in strong
oxidation
by chro-
of lactic
acid.
[5481. Oxi-
(tBuOj2Cr02
was stud-
[549]. The two secondary
be oxidized
selectively
Cr(V1)
was suggested
acid with
methods
(257) could
(Cr03 in aq. H2S04)
PhCONy
of glycerol
considerably
IR spectroscopic
of taxol
and pentane-1,5-diol
were
[547]. The rate of iPrOH
of a termolecular
of oxalic
anion
alcohols
i5451.
i546].
studied
increased
The formation
and less than
of 20 heterocyclic
AcOH were measured
by the 12-tungstatocobaltate(II1) acid
in oxidant
by
and spectrophotometric results 5+ of a complex between V and hydrated benz-
in aqueous
ous perchloric
order
derivatives
Kinetic
The rate of oxidation
[5441.
Groups
and its substituted
to be first
in substrate.
the formation
aldehyde
Functional
with
to yield
Jones's
compound
OH
reagent
(258)
15501.
0 .O--
PhA
0
&i
OCOPh 257
258
In the presence complex
chromate
in CH2C12
solution
or ketones.
of quaternary
salts which
Oxidation
was even more
species
reaction
was performed
fixed this
onto form
nicotinic dichromate
were
catalytic pyridinium [551].
be used
for the conversion
ammonium
-transfer
ammonium
could
applied with
conditions.
efficient
Two new mild,
acid and isonicotinic
complex
ammonium
Cr(V1)
dichromate
quaternary
amounts
and the phase-
chromates could resins
also be
and used
reagents
developed.
were
gave oxidants
into aldehydes
solid-liquid
oxidation
acid were
Cr08
if the
catalytic
CrO8 under
These
or quaternary
and isonicotinium
of alcohols
in only
solid
species,
as homogeneous
suitable
in
based
Nicotinium for the
on
499
oxidation quinones with
of alcohols and thiols
into carbonyl
CrO
and different 3 in 60-80% yield. Thiols
nium oxychromate dichromate tion
oxidized
were
and benzylic
in DMF at 25OC
selective
alcohols
to the corresponding
te in CH2C12
into disulfides
Allylic
with
sieve
carbonyl
(259) was dichroma-
[555].
p”Tg”
5% 0
0
OMe
OMe
260
alcohols
derived
from carbohydrates
to the corresponding
reasonable
for the oxida-
(260) by pyridinium
of 3A molecular
259
be oxidized
with pyridiImidazolium
to the corresponding
-
OH
reagent
2-octanone
The deoxyhexapyranoside
ketone
in the presence
[5531.
into
of 2-octanol
salts gave
oxydichromate
[554].
hydroquinones
Oxidation
ammonium
oxidized
found to be a mild
of allylic
compounds
[552].
quaternary
or pyridinium
was
compounds,
into disulfides
(40-80%)
yields
enones
with
(e.g. 261) could
pyridinium
dichromate
[556].
261
The bisphosphonium found
bichromate
to be a selective
benzylic
primary
aliphatic
nose
each
alcohols
alcohols
Oxidation order
were
acid
References
the corresponding
p. 5 I4
to the corresponding
[558]. Oxidation with ketones
was
of allylic aldehydes.
or Saturated
[557].
by pyridinium
and substrate.
like CH2=C=CMeCH2CH(OH)Ph gave
(Ph3PCH2PPh3)2+(Cr207)2V
for the oxidation
not affected
of D-glucose
in oxidant
and formic
agent
fluorochromate
Reaction
products
of allenic
pyridinium in 71-87%
secondary
chlorochromate yield
is first are arabi-
[5591.
alcohols in CH2C12
Tetrasubsti-
500
tuted were
furans
(262)
oxidized
CR = COOMe,
by pyridinium
COMe;
R' = substituted
chlorochromate
to qive
chenyl)
!Z)+kCEF+CR'OAc
[560]. R
R‘ 262
Me
Treatment reagents cyclic
of the tertiary
results
ethers
strongly
cyclooctenol
in transannular
(264) and
depends
(265). The ratio
on the nature
nium chlorochromate,
Na Cr04, 2
(263) with
oxidative
Me
to the bi-
of the two products
of the Cr(VIj etc.j
Cr(V1)
cyclization
reagent
(Cr03, pyridi-
[561].
Me
Me
I’
,’
0 0
0 263
Kinetic
studies
in acid media to alcohol tion first
264
showed,
and second
of phenoxyacetic order
each
ric, tartaric, the presence additives
that order
of Fe(II), videly aldehyde
alcohol
of Cl-C3
the reaction with
acid with
in oxidant
varied
of the ally1
of the oxidation
or adipic
The unsaturated
265
respect
As(II1)
or Sb(III!.
respect
[5621. Oxida-
in aqueous
AcOH
of cit-
The effect
substrata
by the Mn02
15641.
oxidation
[565].
267
in
of these
COOEt
266
is
by Mn0-4 was studied
on the organic
(267) was prepared
(266) in 72% yield
with
k5631. Oxidation
and sugars
and depended
by Mn(II1)
order
to MniIII!
permanganate
and substrate
acids,
alcohols
is first
501
Aldehydes oxidized
hydroxyl
groups
KMnO 4 to the corresponding
with
95-9890 yield reaction
with protected
using
medium
a mixture
of tBuOH
(e.g. 268) were
carboxylic
and aqueous
acids
in
NaH2P04
as
[566]. CHO ._,OCH2Ph
-
268 Oxidation was
shown
terms;
of simple
to follow
aldehydes
a mixed
only one of these
mixture
order
to carboxylic
acids
rate equation
was substrate
by K2Fe04
containing
dependent
of K2Fe04.A1
0 and CuS04. 5H20 efficiently oxidized allyl2 3' and saturated secondary alcohols to the corresponding
ic, benzylic, aldehydes
or ketones.
inactive
Since
for the oxidation
for selective
oxidations
this
solid mixture
of primary
was practically
alcohols
it could
like that of (269) into
(270)
0
OH
OHOH
be used [568].
The kinetics glycol,
of the oxidation
and tetraethylene
RuC13. nH20 posed
anion
involves
oxidizes
Ph3P to Ph3P0. phines depends
two-electron
tartaric,
References P. 5 I4
acid
(formate
transfer
and glycolic
their ligand
slowly which
the
breaks
is then
up oxi-
[(bp~)~Ru(o)(PEt~) 13-
other
acid
and
tertiary
activity [5701.
phos-
strongly
The kinetics
ion) by [Ru(bpy)2(py)(0)12+
suggest
that oxidation
[5711. Oxidation acid
The pro-
between
to propionic
containing
substrates,
The results
hydride
and a Ru hydride
of the phosphine
of formic
studied.
this complex
Ru(IV)-oxo complex
complexes
diethylene
and using
of a complex
propionaldehyde
organic
on the nature
of oxidation has been
lactic,
Analogous
glycol,
has been determined.
species;
products
to acetone,
also oxidize
of ethylene by [Fe(CN)613-
catalyst
[Fe(CN)6i3- [569]. The iPrOH
(95 %)
the formation
and a Ru(II1)
into the intermediate by
glycol
as homogeneous
mechanism
glycol
dized
three
[5671. A solid
by
occurs
of Na salts
[Fe(CN)6]3-
catalyzed
by a of by
502
Ru(VI)
in aqueous
independent
of
no1 by Ce(S04)2 catalysts.
alkaline
was
the catalytic
effect
of butanol
and substrate A svstem
order
decreased
composed
of
oxidized
ted in aqueous
ent
substituted investigated.
(TPP)CoCl
by
studied.
The rate first
transfer step
expression
'5731. Oxi-
order
in oxidant
acid
The kinetics
was derived
catalyzed of lactic
of oxidation
alcohol
investiga-
solutions.
The reac-
of oxidation
of differ.+ [R~L(OA~)~(H~O)~!
by
radical
oxi-
intermediate
for the oxidation
of propano-
15783.
acid and mandelic
proceeded
radical
[575]. Oxida-
by the one-electron
by Ir(III)
acid by Ni
via C-C bond
and CO2 were detected of aliphatic
in oxidant
from
II cation
ions has been
to a semiquinone
The reaction
primary
3+
leavage;
as products
alcohols
has acet-
15791.
by Ni 3+ is both
and substrate; on outer sphere electron 3+ to Ni was proposed as the rate-determi~ning
[580]. The dimeric
has been
Cu(I1)
synthesized.
(stoichiometric complexes
in two,
The oxidation
mechanism
of Ce(IV)
Both
lenes
seemed
were
quinones
the oxidation HC104.
Ce(IV)
was
of catechols steps
dimedone,
studied
by CuiII)
[581]. and
3,5-dimethyl-2-
!582!. The kinetics
of glyoxylic
acid
and
and pentamminegly-
perchlorate
were investigated in acidic sulfate 2and [Ce(S04)3] appeared to be the oxidant speglyoxalate
while
to be the only oxidant
oxidized
by
oxidation
one-electron
oxidation
Ce(S04)2
for coordinated
Ce(S04)2
of 3,5-di-tert-butyl-o-semiquinone of this complex proves that the
of dihydroresorcin, with
oxalatocobalt(II1) media.
complex
The existence
or catalytic)
proceeds
cyclohexene-l-one
cies
[576].
benzaldehyde,
order
by Co(II1)
The rate was determined
[Fe(CN)6]3-
aldehyde,
the
bnt with Ru04
radicals
1,2- and 1,4_dihydroxybenzenes
The oxidation been
and its
to phenoxy
acid and acetic
in AcOH
of the hydroquinone
[577]. A rate ne-2
as
were different:
in Ru-trichloride
found to be first
phenols
sulfuric
faster
was
dation
Ru04
at high concentrations
by 0~04 was
and
cyclohexa-
and
RuCl3.nH2O
of the two reactions
first
of carboxymethylcellulose
tion was
with
in RuiVI)
of 2-methyl
/574].
[(TPP)Co+']C12 tion
was
is first order
1572]. Oxidation
investigated
The kinetics
rate of oxidation
dation
solution
[Fe(CN)6j3-
with
(NH4)2Ce(N03)6 of D-altrose
No evidence
for free glyoxylic [583!.
1,4_Dimethoxynaphtha-
high para
regioselectivity
under
conditions
mild
by Ce(C104)4
for initial
was
complexation
acid
to l,$-naphtho[584]. Kinetics
studied
in aqueous
was obtained
[585].
of
503 See also
d)
1587, 5961.
Oxidation
of N-containing
Oxidation
of H2NCOCOOH
(oxamic
the unprotonated
substrate
substrate
Second-order
[5861.
of various were
Organic
reacted
Compounds
nitroalkanols -supported
[5871. Nitroketones dissolved
Cr03.
Irradiation
of acetylindoles
nes
[5891.
(272)
showed
that
for the cooxidation
and oxalic were produced
in dichloromethane
Oxidation
K2Cr207
than the protonated
rate constants
2,6-diphenylpiperidin-4-01s
determined
by
acid) faster
with
by ultrasound
acid with
Cr(V1)
by oxidation
of
montmorillonite-
improved
the yield
(271) with Mo05.0P(NMe2)3
gave
-
[588J.
indolo-
R= H, Me,Ph
271
The kinetics by Mn(IV) oxidant
of oxidation
have been
and
studied.
substrate;
-determining
step
of aniline Reactions
hydride
[590].
transfer
Stilbazoles
2- and 4- isomers
underwent
the corresponding
pyridinecarboxylic
tive under
act as an autocatalyst MnOi
in phosphate
cies
formed
buffered MnO2
buffered
solutions
with
HPOi-
were
and H,MnOi
1-Phenylsemicarbazide PhN=NCONH2. studied
and activation by
iFe(bpy)3]3+
of the anilinium
References
p. 5 14
ions
of colloidal
and the kinetics
in the oxidation
of
found
to
by
Mn(IV)
spe-
particles
of this
ion to reaction
were
constants
of substituted with
of
[593].
on the rate
The data correlate
[595]. Oxidation
and
was unreac-
amines
by ferricinium
of substituents
was studied.
was
The
PhCHO
in phosphate
to the surface
is oxidized
The effect energies
to consist
ions bound
Mn02
The soluble
by MnOi
in
as the rate-
to yield
of aliphatic
[5921.
anilines both
by KMn04.
the 3-isomer
Colloidal
of amines
The equilibrium
[594].
acid:
[591].
solutions
shown
oxidized
cleavage
in the oxidation
in the oxidation
first order
was proposed
were
oxidative
the same conditions
and substituted
were
anilines
the pK values
benzylalcohol
or benzyl-
by [Fe!CN)613- in presence of Os(VII1) as catalyst is first order both in oxidant and substrate 1596:. The kinetics of the
amine
Ru(III)-catalyzed been first
oxidation
The reaction
determined. order
of triethanolamine
in the substrate
isoquinolinium
cation
idly oxidized
by
are inhibited
second
in oxidant !597'.
related
5991.
= ‘Nh cc
product.
behave
(273)
Other
similarly
=‘N-Me cc
-
I
are rap-
Both oxidations
ion reaction structures
and both
The 2-methyl-
cation
(274), respectively.
by the ferrocyanide with
(FelCNj6j 3- has
to 2-methyl-l-isoquinolinone
!Fe(CN)6j3-
cations
order
and the catalyst
and the 1-methylquinolinium
and 1-methyl-2-quinolinone
eroaromatic
was
by
1
het!598,
273
0
=1 +; 00
*
274
N
tk
l-Azabicycloalkan-2-ones Oxidation
occured
and afforded ylic
like
regioselectively
either
acid derivatives
(275) were
at the bridgehead
the corresponding like
(276)
oxidized
hydroxy
amino
was performed combination
R’CON
acids
oxidized
(277)
(R = Me,Et;
by Ru04 to give
in a two-phase
system;
276
N
R' = Me,Et,Cy,OEt; lactams
EtOAc/H20
(278). Oxidation
was the best
[601].
A
(CH2),,
Y
-
R’CON
A
(CH21n
v tOOR
277
atom
or carbox-
0
TIJ
were
Ru04.
[600].
275
Cyclic
carbon
compounds
HOOC
n = 1,2,3)
with
dOOR 278
solvent
505
Oxidation (280). Under lactams
of cyclic the
amides
(282) and
cyclic
Ru04
gave cyclic
benzylamines
(2831, and benzamides
r(fH2)tl RCON-CH2
(279) with
same conditions
(284)
[602].
F(fH2)” RCON-C=O
-
lactams
(281) gave
R = H,Me,Ph n = 5,6
280
279 r(CH2)n
p2&l
PhCH2N - CH2
-
282 W2)n rr PhCON - CH2
281 n
q
5,6
Kinetic benzoquinone
data
for the oxidation
by the Co(II1)
the rate-determining the semiquinone
tions
buffer
HEPES
Oxidation
Probably
285 of hydroxypyridines was
studied
the alcoholic
with
to
OH is oxidized
the same condi-
Ce perchlorate
to about
equal
Diastereoselective (289) was achieved
in perchlo-
[6051.
of thianthrene-5-oxide
286
References p. 5 I4
of the substrate
(285) and N,N-dimethylethanol-
of P-, S- or Halogen-containing
Oxidation
esters
that
indicated
H
ric acid medium
leads
to
[co(NH~)~C~IC~~
like EtOH do not react under
[604].
Mo,W)
284
of p-H2NC6H4N(Et)CH2CH20H
complex
by Cu(1).
alcohols
Oxidation
e)
283
step was the conversion
used
are oxidized
but simple
PhCON -C =0
16031.
The widely amine
r(yH2)n +
PhCH2N-C=O
amounts
Organic
(286) with of (287) and
287 CL-hydroxylation
Compounds
(HMPA)MO5 (288)
(M = Cr,
[6061.
288 of the chiral
with MoOg.py.HMPA
carboxylic
in the presence
of
KN(SiMe3j2
and
Hydroxylation
K(sec-BuO).
form of the esters no substituents
and was practically U
at the
carbon
proceeded restricted
atom
over
the enolate
to esters
having
i6071.
289
Oxidation Reaction
of thiocaprolactam
products
were
nism of the permanqanate (290, 291j has been the formation diester
by KMnO4 was
identified
!6081.
ion oxidation
studied.
of thienyl
A rate-determining
of a metallacyclooxetane
(293) was proposed
investigated.
The kinetics
and mecha-
propionates
step
leading
(292) or a cyclic
to
Mn!Vj
16091.
x = H,Br,Me Y = H,D,Me R = H,Me,Ph,CN 291
290 I I
I
-c-c-
m&--cl O--n+
A_
\o
d
1 40 0
0
‘Ml-’ 4 \_
293
292 The pertechnate form Tc(Vj-cystine Oxidation in substrate, was
found
aliphatic during
ion oxidizes
oxidant
the reaction
has been
to iron(III)
agent
examined.
Since
lFe(CNj6,1x-
to
is first
ferrate
order
(K2FeO4j
for the transformation
and sulfones.
Iron(VIj
[612]. The kinetics
leucothionines
acids
f6101.
j611j. Potassium
oxidizing
to sulfoxides
in strong
complexes
by alkaline
and alkali
to be a strong sulfides
L-cysteine
and Tc(Vj-cysteine
of methionine
tion of disulfonated Fe3+
0
(parent
the formation
compound
of
was reduced
of the oxidasee 294) by
of the thionine
skele-
507 ton (295) involves flattening of the phenothiazine moiety, the necessary electron transfer is much more difficult if the organic molecule is a ligand within a metal complex than if it is the anion of an ion pair [613].
Complete oxidation of (H~NCH~CH~S)~ to NH3, carbonate and sulfate by ditelluratocuprate(II1)
in aqueous KOH is catalyzed by
0~04 [614]. Cysteine is quantitatively oxidized to cystine by an excess of the Cu(I1) complex of tris[2-(2-pyridyl)ethyllamine [615]. Triphenyl phosphine was oxidized by (BU~NI[PMO~~O~~I to Ph3PO; the molybdophosphate anion was reduced to [BU~NI~~PMO~~O~~I [6161. 2-Bromo-m-xylene could be oxidized to 2-bromoisophthalic acid by Na2Cr207 at 230°C under 20 bar CO2 pressure [617]. Polymer-supported H2Cr04 was applied for the oxidation of E-C~H~(CH~X)~ (X = Br,Cl,H) to E-C~I-I~(CHO)~ [6181. See also [349, 471, 526, 552, 553, 5701.
7.
Electrooxidation and Photooxidation p -Cyclodextrin accelerates the electrocatalytic oxidation of
NADH by ferrocenecarboxylic acid (Fca). Probably a cyclodextrin-Fca+ complex acts as the effective oxidant [619]. Constant-potential electrolysis of a solution of (TMP)FeOH
in the presence of
olefins was found to produce epoxides as major products [6201. A system consisting of Ru04/Ru02 and Cl+/Cl- redox couples has been developed for the indirect electrooxidation of secondary alcohols to ketones, of primary alcohols and aldehydes to carboxylic acids and of diols to lactones and keto acids. Oxidation proceeds in an aqueous-organic two-phase reaction mixture; Ru04 is the actual oxidant of the organic substrate [621]. The oxo-bridged Ru(III)-
References
p. 5 14
508 dimer
the electrooxidation Actual
solutions. situ
was used
i(bpy)2iH20)RuORu(H20)(bpy)2]4+ of alcohols,
oxidant
[622]. A series
qands
were
catalytic benzene
tested
of Ru complexes
for
in basic
qenerated
dimer
in
bpy and phen
containing
transfer
acids
and amino
was the Ru(IV)Ru(Vj
as electron
oxidation
sugars,
as a catalyst
mediators
li-
in the electro-
of 1,2,4,5_tetramethylbenzene
and pentamethyl-
16231.
D-Fructose
was oxidized
ions under
photochemical
formedwere
reoxidized
to D-erythrose
conditions.
Since
by atmospheric
oxidation
of D-fructuse
could
hydroxide
was precipitated
by Fe(III) Fe(I1)
oxygen,
be performed
or Mn(II1)
and Mn(I1)
thus
the photochemical
catalytically.
from the solutions
No metal
!624].
V. Reviews
Homogeneous
catalysis by transition-metal
complexes.
330 refs.
[625]. Catalysis Recent
by zeolite
developments
Industrial
metal
Organometallic
complex
15 refs.
catalysis
of homogeneous
chemistry
Hydroformylation.
compounds.
in homogeneous
applications
Homogeneous
11 refs.
inclusion
catalyst
[627].
catalysis.
design.
and catalysis
[626].
50 refs.
7 refs.
[629].
in industry.
An old yet new industrial
route
[628].
[630].
to alcohols.
16311.
Asymmetric
hydrosilylation
and hydrocarbonylation.
112 refs.
[632]. Homogeneous
mixed-metal
to N-acyl- a-amino Homogeneous
catalytic
new process
for acetic
Convert Direct
methanol route
from
catalyst
acids
systems:
new and effective
via carbonylations.
reaction
of CO, H2 and methyl
anhydridelvinyl
to ethanol synthesis
21 refs.
acetate.
routes
]633].
acetate:
12 refs.
a
[634].
[635]. gas to ethylene
glycol.
23 refs.
[636].
509
Syntheses gas
of oxygen-containing
in the presence
Metal
carbonyls
Homogeneous 27 refs.
organic
of Rh catalysts.
in phase
and phase
transfer
transfer
compounds
77 refs.
catalysis.
catalyzed
from
synthesis
[6371. 102 refs.
16381.
carbonylation
reactions.
[6391.
Reactivity
of CO in transition
Catalytic
fixation
of carbon
metal dioxide
complexes. by metal
147 refs. complexes.
r6401. 274 refs.
[6411. Reversible
binding
complexes 33 refs.
containing
of transition
initiators
78 refs.
complexes
of Rh(1).
metals
of radical
in conjugation
reduction
with
hydrogen
of trichloromethyl
donors
compounds.
[634].
Syntheses metal
bis ditertiaryphosphine
by cationic
[642].
Carbonyls -
of H2, 02, and CO, and catalysis
and catalytic
complexes.
Supported
actions
25 refs.
metal
complexes
of organosilicon
polymer-supported
[6441. as hydrogenation
catalysts.
206 refs.
[645]. Mechanism tions.
and
stereochemistry
Asymmetric
catalytic
tioselection.
112 refs.
Enantioselective 73 refs. Chiral
hydrogenation:
40 refs.
The applicability tion.
of asymmetric
catalytic
hydrogena-
[646]. mechanism
and origin
of enan-
[6471.
of asynnnetric homogeneous
catalytic
hydrogena-
[6481. catalysis
with
transition
metal
complexes.
[649].
ligands
Application
of organometallic
tion of L-DOPA.
References p. 5 14
for asymmetric
13 refs.
catalysis. catalysis
[651].
163 refs.
c6501.
to the commercial
produc-
Complex the
reducing
agents:
their
19 refs.
field of carbonylations.
Selective
reduction
HRh(PPh3)4.
catalyzed
Catalyzed Effect
synthesis.
electro-organic
electrochemistry.
compounds
Activation
in
in the presence
and their
applications
of
oxidation
type,
-
in electro-
[654]. a modern
chapter
of organic
[655]. of olefinic
reaction
on epoxide
oxygen
and other
53 refs.
by metal
II.
oxidizable
16561.
complexes
oxidation.
as catalysts
hydrocarbons.
conditions
yield.
of liquid-phase
Metalloporphyrins
acid
64 refs.
201 refs.
of molecular
the mechanism
outcome
[652].
by formic
syntheses
liquid-phase
of catalyst
organic
and their
[653].
of Ni compounds
organic
Indirect
of aldimines
9 refs.
Electrochemistry
applications
and its role
119 refs.
in autoxidation
in
!657].
processes.
170 refs.
[658]. Metalloporphyrin-catalyzed
oxygenation
of hydrocarbons.
184 refs.
[659]. Dependence
of activity
and selectivity
for hydroperoxide
epoxidation
carrier.
[66O].
8 refs,
of olefins
The discovery
of the asymmetric
The discovery
of titanium-catalyzed
26 refs.
of asymmetric
catalysts.
104 refs.
Asymmetric
epoxidation
105 refs.
Synthetic 69 refs. A short metric
catalysts
on the structure
epoxidation.
22 refs.
asymmetric
of the
16611.
epoxidation.
[662].
On the mechanism
tion.
of immobilized
aspects
epoxidation
with
titanium-tartrate
16631. of allylic
alcohols:
the Sharpless
epoxida-
[664]. and applications
of asymmetric
epoxidation.
[665]. route
to chiral
oxidation.
sulfoxides
25 refs.
[666].
using
titanium-mediated
asym-
511 83 refs. [6671.
25 Years in the organic chemistry of palladium. The chemistry of activated bleomycin.
58 refs. [6681.
Toward functional models of metalloenzyme active sites: analogue reaction systems of MO 0x0 transferases. Biomimetic oxidations catalyzed by copper.
50 refs. [6691. 49 refs. [6701.
Biomimetic oxidation of hydrocarbons and drugs by metalloporphyrinit systems.
41 refs. [671].
Biological strategies for the manipulation of dioxygen. The chemistry of cytochrome P-450.
34 refs. [672].
List of Abbreviations
acac
acetylacetonate
AS
Annual Survey on Hydroformylation, Reduction, and Oxidation
BPPM
see Fig. (25a)
bpY chiraphos
2,2'-bipyridine see AS 1985, Fig.(g)
COD
1,5-cyclooctadiene
Co(salen)
see Fig. (169)
Co(salpr)
see AS 1985,
CP
cyclopentadienyl
CY DET
cyclohexyl
Fig. (109)
diethyl tartrate
DIOP
see AS 1985,
dipamp
see AS 1985, Fig. (34)
dmgH
dimethylglyoxime
Fig. (31)
dppb
1,4-bis(diphenylphosphino)butane,
Ph2P(CH2)4PPh2
dppe
1,2-bis(diphenylphosphino)ethane,
Ph2PCH2CH2PPh2
dppm
bis(diphenylphosphino)methane,
dppp HD
1,5-hexadiene
HMPA
hexamethylphosphoric triamide
men NBD
menthyl norbornadiene
nmen
neomenthyl
References p. 5 14
Ph2PCH2PPh2
1,3-bis(diphenylphosphino)propane
Ph2P(CH2)3PPh2
512 OEP
2,3,7,8,12,13,17,18-octaethylporphyrinato
0.y.
optical
yield
phen
l,lO-phenanthroline
PY
pyridine
salen
N,N'-bis(salicylidene)-ethylenediamino
SIL
silica
st
stearate,
nC17H35C00
TDCPP
5,10,15,20-tetrakis(2,6-dichlorophenyl)oorphyrin~
TDMPP
5,10,15,20-tetrakis(2,6-dimethylphenyl)porphyrinato
tetpy
2,2':6',2":6",2"'
TMP
5,10,15,20-tetramesitylporphyrinato
-tetrapyridine
TPP
5,10,15,20-tetraphenylporphyrinato
TPP-Me-p
5,10,15,20-tetrakislp-tolyl)porphyrinato
TPP-OMe-p
5,10,15,20-tetrakis(E_methoxyphenyl>porphyrinato
trpy Ts
p-toluenesulfonyl
Z
benzyloxycarbonyl,
Metal
Ti
2,2': 6'2"-terpyridine
79, 183-185, 538
Zr
41, 122,
157,
V
433,
Nb
122
Ta
122
Cr
43, 112-114,
440,
586-588, 100,
200,
109,
1, 190, 403,
562-566, 274,
Re
68, 116,
500,
546,
299,300,
501, 539, 544, 545
372,
409, 510-514,
547-561,
618
200, 223,
293, 343, 354,
502, 503, 515, 343, 344,
371,
540-543,
408, 442-446, 589, 606,
447, 448, 450, 473,
466
607, 616
475-477,
606
410-413, 590-593, 610 123,
473, 474, 495,
200, 258,
476,
494,
243
441, 449,
299, 317,
405,
Tc
254, 257, 265, 280, 316, 429-439,
242,
255, 261,
541, 542, Mn
251,
606, 617,
473, 475, W
PhCH200C-
index
504-506,
MO
(tosyl) p-CH3C6H4S02-
218
318, 320, 450-457, 608,
321, 323-325, 476, 496,
609, 624
357, 382, 383,
497, 516-523,
529,
513
Fe
RU
OS
co
91-93,
98, 102, 267,
406,
410, 412-419,
287, 301,
126, 127,
193,
302, 318, 355-357, 457-468,
479-482,
567-571,
578, 594-599,
7, 9-12,
23, 24, 44, 45, 62, 65-71,
611-613,
117, 124,
128-133,
229,
230, 234,
239, 241, 275, 286,
375,
384,
524,
525, 570,
398, 399,
180-182,
498,
76, 78-82,
469-473,
6, 13, 25-31,
43, 45, 47, 48, 61, 63-68,
370, 372, 376,
530-532,
546,
8, 12-20,
22-24,
197-199,
244-247,
483-486,
490,
471, 487-490,
343,
383, 385-390,
70-73,
77, 81, 83,
231, 233, 347-350,
401,
240, 256,
357,
358,
416, 450,
575, 576, 583 32-42,
83, 89, 100, 103-106, 194,
210, 225,
304, 323-336,
360-364,
224,
346, 374,
603, 614
176, 188-190, 299,
84, 93-102,
201-209,
205, 470,
574, 596,
136-138,
564,
621-623
508, 526-529,
270, 294,
262, 404,
624
297, 322, 345,
5, 23, 24, 84, 101, 134, 135, 187,
268,
383, 396,
499, 507,
186, 195,
407, 420-422,
597, 600-602,
237, 259, 260, 373,
619, 620,
116,
85-88,
Rh
110-115,
266,
208,
49-57,
118, 139-149,
211-215,
250, 269,
68, 69, 72-75,
219,
158-175,
230, 231,
275, 277, 279, 281,
78, 79, 82, 177-179,
191,
234-236,
282, 288, 305-308,
577 Ir
21, 23, 24, 93, 125, 247-249,
Ni
Pd
148, 149, 216,
134, 135,
150, 176,
295, 296, 303,
336,
580
104,
151-156,
108, 121,
272, 273,
276, 278,
338,
423-425,
Pt
2, 22, 46, 58-60,
cu
270, 271, 365-369, 500, 509,
Ag
342, 428
Ce
400,
sm
252, 253,
Eu
283, 298
428,
228, 230,
578
107, 119, 120,
351,
217, 225,
579,
162,
192-194,
220-222,
225,
289-292,
308-315,
319, 337,
491,
492, 499,
90, 156, 198,
383,
230, 238,
338-341, 391-395,
226,
533-536 320
352, 353, 357, 402,
359,
426, 427, 472,
568, 581,
604, 614, 615
483, 531,
537, 573, 582-585,
276, 298
264, 270,
284-286,
296, 311-315, 377-381,
194, 263,
605
493,
514 Lu
3, 298
Y, La, Nd, Gd, Er, Lu U
298
227
Transition
metals,
general
4, 93
References
1
(1986) 2
G.Li,
J.Am.Chem.Soc.
108
612. F-Ding,
F.Dai
(1986)
5911.
CA 105 3
L.Vers1ui.s and V.Tschinke,
T.Ziegler,
H.Rabaa, (1986)
and L.Zhang,
J.-Y.Saillard
Huaxue
and R.Hoffmann,
Xuebao
43 (1985)
J.Am.Chem.Soc.
878;
108
4327.
A.Sevin
and M.Fontecave,
K.A.Jorgensen
J.Am.Chem.Soc.
and R.Hoffmann,
J.L.Costa,
A.Demonceau,
P.Teyssie,
Acta
J.Am.Chem.Soc.
J.Drapier,
Chim.Hunq.
108 (1986)
108 (1986)
A.Hubert,
119 (1985)
3266.
A.Noel
1867.
and
147; CA 104 (1986)
132660. 7
I.W.Shim, CA 104
V.D.Mattera
(1986)
8
H.W.Bosch
9
Y.Kiso,
and W.M.Risen,
J.Catal.
94 (1985)
and B.B.Wayland,
M.Tanaka,
J.C.S.Chem.Commun.
H.Nakamura,
J.Organomet.Chem.
312
(1986)
T.Yamasaki
(1986)
357.
Y.Kiso
and K.Saeki,
J.Orqanomet.Chem.
309 (1986)
C26.
11
Y.Kiso
and K.Saeki,
J.Organomet.Chem.
303 (1986)
C17.
12
R.Whyman,
13
Am.Chem.Soc
900.
and K.Saeki,
10
(1986)
531;
19312.
.,Div.Pet.Chem.
31 (1986)
32; CA 104
226654.
T.Masuda,
K.Murata
and A.Matsuda,
Bull.Chem.Soc.Jpn.
59(1986)
1287. 14
G-Van (1986)
15
der
Lee and V.Ponec,
J.Catal.
99 (1986)
511; CA 105
45196.
W.M.H.Sachtler, 513; CA 105
D.F.Shriver
(1986)
45197.
and M.Ichikawa,
J.Catal.
99
(1986)
515
16
T.Masuda, K.Murata, T.Kobayashi and A.Matsuda, Bull.Chem. Soc.Jpn. 59 (1986) 2349.
17
H.Tanaka, Y.Hara, E.Watanabe, K.Wada and T.Onoda, J.Organomet.Chem. 312 (1986) C71.
18
M.Tamura, M.Ishio, T.Deguchi and S.Nakamura, J.Organomet. Chem. 312 (1986) C75.
19
E.Watanabe, Y.Hara, K.Wada and T.Onoda, Chem.Lett. (1986) 285.
20
E.Watanabe, K.Murayama, Y.Hara, Y.Kobayashi, K.Wada and T.Onoda, J.C.S.Chem.Commun.
21
(1986) 227.
T.Takano, T.Deguchi, M.Ishino and S.Nakamura, J.Organomet. Chem. 309 (1986) 209.
22
M.Rijper, M.Schieren and A.Fumagalli, J.Mol.Catal. 34 (1986) 173.
23
J.A.Marsella and G.Pez, J.Mol.Catal. 35 (1986) 65.
24
J.A.Marsella and G.P.Pez, Prepr.-Am.Chem.Soc.,Div.Pet.Chem 31 (1986) 22; CA 104 (1986) 188631.
25
J.Krupcik and D.Repka, Collect.Czech.Chem.Commun. 1808;
50 (1985
CA 104 (1986) 28196.
26
J.Kolena, Chem.Prum. 35 (1985) 300. CA 104 (1986) 129210.
27
V.Macek and R.Kubicka, Ropa Uhlie 28 (1986) 164; CA 105 (1986) 45198.
28
Y-Sun, D.Zhang, Z.Zhao, W.Zhai, Y.Ma, Z.Wang, Y-Ma and D.Li, Shiyou Huagong 15 (1986) 372; CA 105 (1986) 193293.
29
Yu.B.Kagan, O.L.Butkova, G.A.Korneeva and S.M.Loktev, Izv. Akad.Nauk SSSR, Ser.Khim. (1985) 1714; CA 105 (1986) 42292.
30
M.K.Markiewicz and M.C.Baird, Inorg.Chim.Acta 113 (1986) 95.
31
J.Collin, C.Jossart and G.Balavoine, Organometallics 5 (1986) 203.
32
K.Doyama, T.Joh, S.Takahashi and T.Shiohara, Tetrahedron Lett. 27 (1986) 4497.
33
S.Li, W.Yuan, D.Liu, W.Pan and J.Liu, Wuli Huaxue Xuebao 2 (1986) 77; CA 105 (1986) 135863.
34
A.J.Abatjouglu and D.R.Bryant,Arabian J.Sci.Eng. 10 (1985) 427; CA 105 (1986) 208282.
516 35
W.E.Smith,
G.R.Chambers,
G.E.Harrison 151; CA 105 36
A.M.Trzeciak
38
A.A.Bahsoun (1986)
and R.Ziessel,
P.Escaffre,
P.Kalck,
A.Thorez,
J.Mol.Catal.
Nouv.J.Chim.
P.Kalck,
J.
34 (1986)
9 (1985)
B.Besson,
J.Organomet.Chem. F.Serein
D.C.Park,
F.Senocq,
302
213.
225; CA 104
R.Perron
and
(1986) C17.
and A.Thorez,
C.Randrianalimanana, J.Mol.Catal.
K.Prbkai-Tatrai,
J.Mol.Catal.
36
A.Thorez, 35 (1986)
S.Tijrijsand B.Heil,
P.Kalck,
R.Choulaoun
213. J.Organomet.Chem.
315
231. Ind.Eng.Chem.Prod.Res.Dev.
E.R.Tucci, (1986)
44
Eldik,
349.
(1986) 43
and R.van
337.
and J.J.Ziolkowski,
and D.Gervais, 42
A.J.Dennis,
22 (1985)
13991.
(1986) 41
S.Aygen
J.J.Zidlkowski,
Y.Colleuille, 40
J.N.Cawse,
Chem.Ind,(Decker)
133314.
34 (1986)
Mol.Catal.
39
(1986)
A.M.Trzeciak,
37
R.C.Lindberg,
and D.R.Bryant,
25 (1986)
27; CA 104
111757.
E.M.Gordon
and R.Eisenberg,
J.Organomet.Chem.
306
(1986)
c53. 45
M.Hidai, (1986)
46
P.W.N.M.
van Leeuwen,
48
S.Zhang,
307
51
J.Mol.Catal.
35
J.M.Herman,
S.E.Moore,
K.D.Lavin
P.E.Garrou
P.J. Van Den Berg
H.Li,
B.He,
14 (1985)
Y.Luo
and H.Fu,
J.Organomet.
and H.R.Allcock,
and R.A.Dubois,
259; CA 105 (1986)
32 (1986)
Huaqonq
and J.H.G.
Organo-
460.
J.(Lausanne) J.San,
N.Wu,
R.L.Wife 31.
65.
P.E.Garrou,
19 (1985)
(1986)
A.Zhang,
5 (1986)
D.L.Hunter, Catal.
50
(1986)
R.A.Dubois, metallics
49
G.F.Roobeek,
J.C.S.Chem.Commun.
Y.Wang, Chem.
and Y.Uchida,
29.
Frijns, 47
Y.Koyasu
A.Fukuoka,
and J.J.F.Scholten,
101; CA 105
X.Yang,
X.Wang
390; CA 104
Appl.
96829.
(1986)
26116.
and Q.Zhou,
(1986)
Chem.Enq.
209125.
Shiyou
517
52
B.He, F.Zheng, J.Sun, H.Li, Q.Zhou, G.Liu, X.Yang and C.Fu, Cuihua Xuebao 6 (1985) 296; CA 104 (1986) 198737.
53
D.L.Hunter, S.E.Moore, A.R.Dubois, P.E.Garrou, Appl.Catal. 19 (1985) 275; CA 105 (1986) 60142.
54
F.R.Hartley, S.G.Murray and A.T.Sayer, J.Mol.Catal. 38 (1986) 295.
55
E.J.Rode, M.E.Davis and B.E.Hanson, J.Catal. 96 (1985) 563; CA 105 (1986) 60186.
56
R.J.Davis, J.A.Rossin and M.E.Davis, J.Catal. 98 (1986) 477; CA 105 (1986) 42230.
57
E.J.Rode, M.E.Davis and B.E.Hanson, J.Catal. 96 (1985) 574; CA 104 (1986) 185796.
58
C.Pan, Y.Zhao, Y.Chen, Zhongguo Kexue Jishu Daxue Xuebao 15 (1985) 439; CA 105 (1986) 208287.
59
J.K.Stille, Chem.Ind.(Decker) 22 (1985) 23; CA 104 (1986) 129560.
60
G.Parrinello, R.Deschenaux and J.K.Stille, J.Org.Chem. 51 (1986) 4189.
61
Z.Zhang, X.Wang, W.Zhao, S.Zhang, Y.Fang and B.Na, Huaxue Xuebao 44 (1986) 506; CA 105 (1986) 90126.
62
G.Braca, A.M.Raspolli Galletti and G.Sbrana, Prepr.-Am.Chem. sot., Div.Pet.Chem. 31 (1986) 104; CA 105 (1986) 8303.
63
Y.Sugi, K.Takeuchi, H.Arakawa, T.Matsuzaki and K.-I.Bando, Cl Mol.Chem. 1 (1986) 423.
64
E.Lindner, C.Scheytt and P.Wegner, J.Organomet.Chem. 308 (1986) 311.
65
W.Strohmeier, H.HBcker and G.Sommer, Cl Mol.Chem. 1 (1986) 475.
66
E.Lindner, H.A.Mayer and P.Wegner, Chem.Ber. 119 (1986) 2616.
67
E.Lindner, A.Sickinger and P.Wegner, J.Organomet.Chem. 312 (1986) C37.
68
T.Matsuzaki, Y.Sugi, H.Arakawa, K.Takeuchi, K.Bando and N.Isogai, Chem.Ind.(London)(l985)555; CA 104 (1986) 148255.
518 69
314
metal.Chem. 70
71
(1986)
G.Bitsi
G.Jenner,
(1986)
K.Watanabe,
K.Kudo,
J.Organo-
227. Appl.Catal.
24 11986)
100106. S.Mori
and N.Sugita,
Bull.Chem.Soc.Jpn.
2565. F.Hugues
D.Commereuc,
Y.Chauvin, Catal.
and T.A.Pakkanen,
and P.Andrianary,
319; CA 105
59 (1986) 72
K.Karjalainen
J.Purdianinen,
34 (1986)
73
M.Marchionna
74
T.Okano,
and D.Prouteau,
J.Mol.
275.
and G.Longoni,
J.Mol.Catal.
H.Konishi
M.Makino,
35 (1986)
and J.Kiji,
107.
Chem.Lett.
(1985)
1793. 75
T.Okano,
H.Ito,
H.Konishi
and J.Kiji,
Chem.Lett.
(1986)
1731. 76
J.R.Zoeller,
77
R.W.Wegman
78
E.Drent,
79
G.Braca, Catal.
J.Mol.Catal. and D.C.Busby,
37 (1986)
377.
J.C.S.Chem.Commun.
J.Mol.Catal.
37 (1986)
93.
A.M.Raspolli
Galletti,
G.Sbrana
34 (19861
J.R.Zoeller,
81
G.Jenner
and P.Andrianary,
a2
E.Drent,
Prepr.-Am.Chem.Soc.,Div.Pet.Chem.
a3
a4
a5
86
J.Mol.
37 (1986)
117.
J.Orqanomet.Chem.
307 (1986) 31 (1986)
263.
97;
and G.Jenner,
J.Organomet.Chem.
310
115.
D.S.Sarratt (1986)
and F.Zanni,
188634.
H.Kheradmand
G.Bitsi, (1986)
J.Mol.Catal.
(1986)
332.
183.
80
CA 104
(1986)
and D.J.Cole-Hamilton,
J.Organomet.Chem.
306
c41.
M.S.Borovikov
and V.A.Ryabkov,
CA 104
224526.
(1986)
I.Kovacs,
F.Ungvary
Kinet.Katal.
and L.Mark6,
27 (1986)
Organometallics
319;
5 (1986)
209. a7
F.Ungvbry
88
R.A.Dubois and P.E.Garrou,
and L.Mark6,
Organometallics
5 (1986)
Organometallics
2341.
5 (1986)
466.
519 89
E.V.Slivinskii,
Yu.B.Kagan,
R.A.Aranovich, Neftekhimiya 90
A.Scrivanti,
91
C.Pac,
92
93
94
A.Berton,
L.Toniolo
(1986)
S.Nakamura,
90 (1986)
5244: CA 105
97
(1986)
T.Venalainen,
E.Iiskola, J.Mol.Catal.
4140.
H.Ishida,
K.Tanaka, 5 (1986)
98
D.C.Gross
and P.C.Ford,
99
Y.Shvo
112 101
T.A.Pakkanen
and
and T.T.Pakkanen,
T.T.Pakkanen
O.Weir
M.Morimoto
and E.Iiskola,
and J.G.Vos,
Inorg.Chem.
and T.Tanaka,
J.Am.Chem.Soc. J.Organomet.Chem.
G.Zassinovich
(1986)
T.A.Pakkanen 293.
Organo-
724.
and D.Czarkie,
G.Clauti,
J.Phys.Chem.
314 (1986) C49.
metallics
100
and S.Kagawa,
305.
W.Hinrichs,
25 (1986)
J.C.S.
159429.
34 (1986)
T.A.Pakkanen,
J.G.Haasnoot,
J.Organo-
and H.Sakurai,
J.Pursiainen,
E.Iiskola, 34 (1986)
J.Organometal.Chem. 96
S.Yanagida
H.Kusano
T.T.Pakkanen,
T.Venalainen,
and C.Botteghi,
1115.
M.Iwamoto,
T.Venalainen,
and S.M.Loktev, 56974.
369.
T.Matsuo,
(1986)
J.Mol.Catal. 95
791; CA 104 (1986)
K.Miyake,
Chem.Commun.
G.A.Korneeva,
N.N.Rzhevskaya
25 (1985)
314
metal.Chem.
V.I.Kurkin,
I.G.Fal'kov,
and G.Mestroni,
108 315
(1986)
6100.
(1986) C25.
Inorg.Chim.Acta
103.
R.A.Sanchez-Delgado
and A.Oramas,
J.Mol.Catal.
36 (1986)
283. 102
C.Crotti,
S.Cenini,
J.C.S.Chem.Commun. 103
T.Kitamura CA 104
B.Rindone, (1986)
and T.Joh,
(1986)
S.C.Shim,
K.N.Khoi
105
K.Kaneda,
M.Kobayashi,
106
Kaishi
K.Takeuchi, Cl Mol.Chem.
and F.Demartin,
Nippon
Kagaku
Kaishi
(1985)
473;
Chem.Lett.
(1986)
1149.
108626.
104
Kagaku
S.Tollari
784.
and Y.K.Yeo,
(1985)
Y.Sugi,
T.Imanaka
and S.Teranishi,
494; CA 104 (1986) T.Matsuzaki,
1 (1986)
407.
Nippon
147887.
H.Arakawa
and K.-I.Bando,
520 107
P.Giannoccaro (1986)
108
N.K.Eremenko
A.I.Min'kov, SSSR
109
and E.Pannacciulli,
Inorg.Chim.Acta
117
69.
283
(1985)
and O.A.Efimov,
160; CA 105
R.Sapienza,
W.Slegeir
249; CA 104
(1986)
(1986)
Dokl.Akad.Nauk
6243.
and D.Mahajan,
Polyhedron
5 (1986)
209135.
110
K.Ogura
and I.Yoshida,
J.Mol.Catal.
34 (1986)
309.
111
K.Ogura
and I.Yoshida,
J.Mol.Catal.
34 (1986)
67.
112
K.Ogura
and M.Takagi,
Electrochem. 113
K.Ogura
(1986)
(1986)
(1986)
J.C.S.Dalton
Trans.
50672. (1985)
2499:
185795. 16 (1986)
J.Appl.Electrochem.
K.Ogura,
Chem.Interfacial
359; CA 105
and S.Yamazaki,
CA 104 114
201
J.Electroanal
732; CA 105 (1986)
160782. 115
M.Nakazawa,
Y.Mizobe,
Y.Matsumoto,
Bull.Chem.Soc.Jpn.
M.Hidai, 116
H.Kukkanen
117
R.Maidan,
and I.Willner,
T.Fukaya,
M.Kodaka
118
Hokoku 119
and T.Pakkanen,
81 (1986)
D.J.Pierce
120
and M.Sugiura,
197 (1986)
C.L.Bailey, Chim.Acta
121
Y.Fujiwara,
Tetrahedron
Lett.
123
W.D.Jones
and M.Fan,
124
H.Suzuki,
D.H.Lee,
Chem.
(1986) C45.
126
(1986)
Kagaku
D.P.Rillema
H.Taniguchi,
and R.M.Zubyk,
C.J.Cameron,
R-Davis,
108
(1986) L43.
(1986)
Gijutsu
8100.
Kenkyusho
180378.
J.Electroanal.Chem.Interfacial
27 !1986)
W.A.Nugent
E.Guittet,
and
77520.
and R.Nowak,
Inorg.
116 (1986) L45.
122
125
114
317; CA 104 (1986)
R.D.Bereman,
Y.Morimoto,
317
J.Am.Chem.Soc.
255; CA 105 (1986)
M.Tezuka
809.
Inorg.Chim.Acta
and D.Pletcher,
Electrochem.
Y.Uchida,
59 (1986)
Organometallics
H.Felkin,
N.M.S.Khazaal 1387.
25 (1986) 5 (1986)
and Y.Moro-oka,
T.Fillebeen-Khan,
J.C.S.Chem.Commun.
and Y.Nagano,
1809.
Inorg.Chem.
N.Oshima
Y.Hori
4604.
1057.
J.Organomet.
N.J.Forrow
and
(1986) 801.
and V.Maistry,
J.C.S.Chem.Commun.
521
125
'C.J.Cameron, H.Felkin, T.Fillebeen-Khan, N.J.Forrow and EdGuittet, J.C.S.Chem.Commun. (1986) 801.
126
R.Davis, N.M.S.Khaz.aal and V.Maistry, J.C.S.Chem.Commun. (1986) 1387.
127
H.Inoue, Y.Nagao and E.Haruki, Chem.Express 1 (1986) 165; CA 105 (1986) 152489.
128
C.Bello,L.L.Diosady, W.F.Graydon and L.J.Rubin,JAOCS, J. Am.Oil Chem.Soc. 62 (1985) 1587; CA 104 (1986) 18813.
129
J.A.Smieja, J.E.Gozum and W.L.Gladfelter, Organometallics 5 (1986) 2154.
130
J.L.Zuffa, M.L.Blohm and W.L.Gladfelter, J.Am.Chem.Soc. 108 (1986) 552.
131
B.He, K.Teng, J.Sun and H.Li, Yingyong Huaxue 2 (1985)(4) 31; CA 104 (1986) 96414.
132
Y.Doi, K.Yano, A.Yokota,H.Miyake and K.Soga, Int.Congr. Catal., 8th (1984) IV689; CA 105 (1986) 121563.
133
L.N.Lewis, J.Am.Chem.Soc. 108 (1986) 743.
134
J.L.Zuffa and W.L.Gladfelter, J.Am.Chem.Soc. 108 (1986) 4669.
135
M.Castiglioni, R.Giordano, E.Sappa, A.Tiripicchio and C.M.Tiripicchio, J.C.S.Dalton Trans. (1986) 23; CA 105 (1986) 97657.
136
L.I.Gvinter, L.N.Suvorova, S.S.Danielova and L.Kh.Freidlin Zh.Org.Khim. 22 (1986) 79; CA 105 (1986) 209215.
137
G.C.Pillai, J.W.Reed and E.S.Gould, Inorg.Chem. 25 (1986) 4734.
138
G.C.Pillai and E.S.Gould, Inorg.Chem. 25 (1986) 4740.
139
E.E.Nifantyev, A.T.Teleshev, G.M.Grishina and A.A.Borisenko, Phosphorus Sulfur 24 (1985) 333; CA 104 (1986) 60958.
140
M.M.Taqui Khan, B.Taqui Khan, S.Begum and S.Mustafa Ali J.Mol.Catal. 34 (1986) 283.
141
J.A.Heldal and E.N.Frankel, JAOCS, J.Am.Oil Chem.Soc. 62 (1985) 1117; 104 (1986) 148064.
522 142
S.A.Preston,
143
M.Zuber, (1986)
144
W.A.Szuberla
J.Azran,
O.Buchman,
V.N.Kalinin,
SSSR,
147
F.Lu,
and F.P.Pruchnik,
I.Amer
O.A.Mel'nik,
977.
J.Mol.Catal.
and J.Blum,
J.Mol.Catal.
(1985)
38
34
D-Wang
Y.Wang,
and
(1986)
V.Zbirovsky
and M.Capka,
836; CA 105
(1986)
Khan,
T.M.Frunze,
and V.Z.Sharf,
2442: CA 105 (1986)
154; CA 104
M.M.Taqui
A.A.Sakharova,
N.V.Borunova
Ser.Khim.
(1986) 148
and
(1986)
229.
L.I.Zakharkin,
146
J.C.S.Chem.Commun.
309.
(1986) 145
P.Palma-Ramirez
D.C.Cupertino,
D.J.Cole-Hamilton,
Y.Yu,
Gaofenzi
Izv.Akad.Nauk 226929.
Tongxun
(1985)
19914. Collect.Czech.Chem.Commun.
(1986)
B.Taqui
51
226955.
Khan and S.Begum,
J.Mol.Catal.
34
9.
149
R.H.Crabtree
150
K.M.Ho,
and M.W.Davis,
M.C.Chan
J.Orq.Chem.
and T.Y.Luh,
51 (1986)
Tetrahedron
Lett.
2655.
21 (1986)
5383. 151
L.V.Mironova,
Yu.S.Levkovskii,
N.A.Ivanova,
G.V.Ratovskii,
Koord.Khim. 152
11 (1985)
E.A.Bekturov,
L.B.Belykh,
E.I.Dubinskaya
1689; CA 104 (1986)
S.E.Kudaibergenov,
A.K.Zharmagametova, Makromol.Chem.,
Commun.
and F.K.Shmidt, 40520.
D.V.Sokol'skii,
S.G.Mukhamedzhanova
Rapid
G.V.Lobza,
7 (1986)
and A.Sh.Kuanyshev, 187; CA 104 (1986)
206675. 153
E.A.Bekturov,
S.E.Kudaibergenov,
D.V.Sokolskii,
A.K.Zharmagambetova
React.Polym.,Ion (1986) 154
Exch.,
G.A.Sytov,
and N.S.Nametkin,
155
(1986)
K.R.Kumar, Catal., 129298.
and N.V.Anisimova,
Sorbents
4 (1985)
49; CA 104
110900.
V.N.Perchenko,
CA 104
S.S.Saltybaeva,
R.Sh.Abubakirov,
Dokl.Akad.Nauk.SSSR
T.O.Omaraliev
282 (1985)
109;
129521.
B.M.Choudary,
M.Z.Jamil
(Proc.Natl.Symp.Catal.)
and G.Thyaqarajan,
7th (1985j 71; CA 104
Adv. (1986)
523
156
I.Feinstein-Jaffe and A.Efraty, J.Mol.Catal. 35 (1986) 285.
157
R.Choukroun, M.Basso-Bert and D.Gervais, J.C.S.Chem.Commun. (1986) 1317.
158
F.Pruchnik, B-R-James and Kvintovics, Can.J.Chem. 64 (1986) 936.
159
H.Takaya, K.Mashima, K.Koyano, M.Yagi, H.Kumobayashi, T.Taketomi, S.Akutagawa and R.Noyori, J.Org.Chem. 51 (1986) 629.
160
J.M.Brown, L.Cutting, P.L.Evans and P.J.Maddox, Tetrahedron Lett. 27 (1986) 3307.
161
H.Brunner, A.Knott, M.Kunz and E.Thalhammer, J.Organomet. Chem. 308 (1986) 55.
162
C.Fuganti, P.Grasselli, L.Malpezzi and P.Casati, J.Org. Chem. 51 (1986) 1126.
163
J.M.Nuzillard, J.C.Poulin and H.B.Kagan, Tetrahedron Lett. 27 (1986) 2993.
164
F.Alario, Y.Amrani, Y.Colleuille, T.P.Dang, J.Jenck, D.Morel and D.Sinou, J.C.S.Chem.Commun. (1986) 202.
165
T.Minami, Y.Okada, R.Nomura, S.Hirota, Y.Nagahara and K.Fukuyama, Chem.Lett. (1986) 613.
166
W.Zhong, R.Li, J.Zhang, L.Weng, Y.Shi and H.Feng, Tianjin Daxue Xuebao (1985) (2) 99; CA 105 (1986) 42927.
167
D.Sinou and Y.Amrani, J.Mol.Catal. 36 (1986) 319.
168
S.Saito, Y.Nakamura and Y.Morita, Chem.Pharm.Bull. 33 (1985) 5284; CA 105 (1986) 79250.
169
A.Kinting and H.-W.Krause, J.Organomet.Chem. 302 (1986) 259.
170
U.Nagel, E.Kinzel, J.Andrade and G.Prescher, Chem.Ber. 119 (1986) 3326.
171
U.Nagel and E.Kinzel, Chem.Ber. 119 (1986) 1731.
172
U.Nagel and E.Kinzel, J.C.S.Chem.Commun.
173
M.Yamashita, M.Kobayashi, M.Sugiura, K.Tsunekawa,
(1986) 1098.
T.Oshikawa, S.Inokawa and H.Yamamoto, Bull.Chem.Soc.Jpn. 59 (1986) 175.
524 114
R.Selke
175
R.Selke,
176
W.Guo,
Y.Chen
and Y.Ma,
CA 104
(1986)
207811.
177
and H.Pracejus,
178
D.G.Allen,
183
184
186
188
P.Frediani,
J.Am.Chem.Soc.
L.A.Paquette,
G.Pfeiffer
and
Organometallics
5
Tetrahedron
Yi Hsiao,
Lett.
J.A.McKinney,
P.Le Coupanec
(1985)
T.Ohta
and
Lett.
and
27 (1986)
5599.
and P.H.Dixneuf,
J.Orqanomet.
C35.
T.Feng
and Y.Zhou,
CA 104
(1986)
M.O.Albers,
173009.
(1986) 7117. M.L.McLaughlin
B.Demerseman,
and M.Bianchi,
(1986)
M.Kitamura,
108
Tetrahedron
287
G.Menchi
53; CA 105
A.L.Rheingold,
Tongji
Daxue
Xuebao
(1984)
(4) 79;
19248.
E.Sinqleton
and M.M.Viney,
J.Mol.Catal.
34
235.
R.A.Sanchez-Delgado,
A.Andriollo,
V.Leon
and J.Espidel,
CA 104
(1986)
L.I.Cvinter,
J.C.S.Dalton
E.Gonzales, Trans.
N.Valencia,
(1985)
1859;
33647. V.M.Ignatov,
and V.S.Sharf,
V.Yu.Egorova, Neftekhimiya
L.N.Suvorova, 26 (1986)
37; CA 105
190426.
H.Kanai,
Y.Watabe
and T.Nakayama,
Rull.Chem.Soc.Jpn.
59
1277.
J.F.Garst, (1986)
312
93.
U.Matteoli,
68 (1986)
M.Ohta,
(1986)
190
(9) 16;
5497.
R.Noyori,
(1986)
G.Buono,
317 (1986)
and G.Simonneaux,
H.Takaya,
P.S.Belov
189
(1985)
J.Organomet.Chem.
and D.L.Wood,
P.Le Maux
F.Piacenti,
(1986) 187
Tongbao
213.
1009.
V.Massoneau,
Chem. 185
Huaxue
F.Petit,
S.B.Wild,
Chim.Ind.(Milan) 182
227.
and F.Petit,
A.Mortreux,
27 (1986) 181
37 (1986)
J.Organomet.Chem.
(1986) 180
A.Mortreux
37 (1986)
375.
A.Karim, C.Siv,
179
J.Mol.Catal.
A.Karim, (1986)
J.Mol.Catal.
T.M.Bockman
1689.
and R.Batlaw,
J.Am.Chem.Soc.
108
525 191
V.Zbirovsky, H.J.Kreuzfeld and M.Capka, React.Kinet.Catal. Lett. 29 (1985) 243; CA 104 (1986) 231278.
192
O.P.Parenago, G.M.Cherkashin and L.P.Shuikina, Neftekhimiya 25 (1985) 589; CA 105 (1986) 133300.
193
R.V.Honeychuck, M.O.Okoroafor, L.-H.Shen and C.H.Brubaker, Organometallics 5 (1986) 482.
194
E.Bayer and W.Schumann, J.C.S.Chem.Commun.
(1986) 949.
195
V.F.Pechenkina, R.A.Rustambekova, B.Zh.Zhanabeev and A.M.Ashirov, Izv.Vyssh.Uchebn.Zaved.,Khim.IZhim.Tekhnol. 28 (1985) 59; CA 105 (1986) 114630.
196
V.F.Pechenkina, D.V.Sokol'skii, B.Zh.Zhanabaev and A.M.Ashirov, Izv.Vyssh.Uchebn.Zaved.,Khim.Khim.Tekhnol. 28 (1985) 54; CA 105 (1986) 60325.
197
I.Amer, H.Amer, and J.Blum, J.Mol.Catal. 34 (1986) 221.
198
A.G.Dedov, A.S.Loktev, V.S.Pshezhetskii and E.A.Karakhanov, Neftekhimiya 25 (1985) 452; CA 105 (1986) 190506.
199
E.A.Karakhanov, E.B.Neimerovets, V.S.Pshezhetskii and A.G.Dedov, Khim.Geterotsikl.Soedin.
(1986) (3) 303;
CA 105 (1986) 23811. 200
P.A.Tooley, C.Ovalles, S.C.Kao, D.J.Darensbourg and M.Y.Darensbourg, J.Am.Chem.Soc. 108 (1986) 5465.
201
M.Tanaka, T.Sakakura, T.Hayashi and T.-A.Kobayashi, Chem. Lett. (1986) 39.
202
K.Hotta, Nippon Kagaku Kaishi (1985) 674; CA 104 (1986) 6028.
203
T.Suarez, B.Fontal and D.Garcia, J.Mol.Catal. 34 (1986) 163.
204
Y.Shvo, D.Czarkie, Y.Rahamin and D.F.Chodosh, J.Am.Chem. sot.
205
108 (1986) 7400.
R.A.Sanchez-Delgado, N.Valencia, R.-L.Marquez-Silva, A.Andriollo and M.Medina, Inorg.Chem. 25 (1986) 1106.
206
U.Matteoli, G.Menchi, M.Bianchi and F.Piacenti, J.Organomet.Chem. 299 (1986) 233.
207
U.Matteoli, G.Menchi, M.Bianchi, P.Frediani and F.Piacenti, Gazz.Chim.Ital. 115 (1985) 603; CA 104 (1986) 224426.
526 208
J.F.Knifton
209
Y.Ishii, Lett.
211
S.T&zos,
213
214
and H.Alper,
T.Kogure (1986)
H.Takahashi,
215
K.Tani, (1986)
216
217
Acta
Chim.Hunq.
119
208285. Organometallics
and Y.Yoda,
5 :1986)
Org.Synth.
63 (1985)
1909. 18;
Lett.
M.Chiba,
27 (1986) Y.Tatsuno
E.Tanigawa,
T.Morimoto
and K.Achiwa,
4477. and S.Otsuka,
Chem.Lett.
737.
E.Farnetti,
M.Pesce,
M.Graziani,
J.C.S.Chem.Commun.
(1986)
G.I.Korenyako,
J.Kaspar,
I.G.Iovel
Yu.Sh.Goldberg, Commun.
218
Tetrahedron
68661. M.Hattori,
Tetrahedron
387.
823.
and L.Markd,
135; CA 105 (1986)
I.Ojima, CA 104
and S.Yoshikawa,
59 (1986)
L.Kollar
B.Heil,
H.A.Zahalka
1 (1986)
365.
Bull.Chem.Soc.Jpn.
K.Mita,
(1985)
Cl Mol.Chem.
M.Saburi
T.Ikariya,
27 (1986)
210
212
and J.J.Lin,
R.Spogliarich (1986) 746.
and M.V.Shymanska,
J.C.S.Chem.
286. O.M.Negomedzyanova,
V.M.Belousov,
and
K.V.Kotegov
22 (1984)
Katal.Katal.
and
98; CA 104
(1986)
50596. 219
E.G.Leelamani, Adv.Catal. (1986)
220
221
222
(Proc.Natl.Symp.Catal.)
P.K.Santra
(1985)
Ser.Khim.
and M.V.Klyuev,
(1985)
97; CA 104
C.J.Casewit,
D.E.Coons, DuBois,
CA 104
L.L.Wright,
G.Siiss-Fink and G.Herrmann,
225
W.Oppolzer, R.J.Mills 183.
SSSR,
Ser.
E.S.Levitina, Izv.Akad.Nauk.SSSR,
(1986)
Organometallics
224
224414.
171933.
E.I.Karpeiskaya,
2157;
(1986)
Izv.Akad.Nauk
(1986)
and L.N.Kaigorodova,
(1985)
M.Rakowski
(1986)
and G.K.N.Reddy,
Proc.Indian Natl.Sci.
538; CA 104
1716; CA 105
E.I.Klabunovskii, L.F.Godunova
223
7th
and C.R.Saha,
Part A 51 (1985)
A.D.Pomogailo, Khim.
V.Gayathri
129299.
P.Khandual, Acad.,
N.Shashikala,
207626. W.K.Miller
5 (1986)
Angew.Chem.
and
951.
98 (1986)
and M.Reglier, Tetrahedron
568.
Lett.
27
527 226
R.M.Williams, D.Zhai and P.J.Sinclair, J.Org.Chem. 51 (1986) 5021.
227
G.B.Deacon, T.D.Tuong and G.R.Franklin, Inorg.Chim.Acta l_ll (1986) 193.
228
R.H.Grabtree, M.J.Burk, R.P.Dion, E.M.Holt, M.E.Lavin, S.M.Morehouse, C.P.Parnell and R.J.Uriarte, Chem.Ind. (Decker) 22 (1985) 37; CA 105 (1986) 24438.
229
I.Minami, M.Yamada and J.Tsuji, Tetrahedron Lett. 27 (1986) 1805.
230
T.Yamakawa, H.Miyake, H.Moriyama, S.Shinoda and Y.Saito, J.C.S.Chem.Commun.
231
(1986) 326.
S.K.Tyrlik, A.Korda and A.Gieysztor, J.Mol.Catal. 34 (1986) 313.
233
s.wu, F.Luo, Y.Teng and G.Li, Yingyong Huaxue 2 (1985) (2) 43; CA 104 (1986) 148602.
234
Y.Ishii, K.Osakada, T.Ikariya, M.Saburi and S.Yoshikawa, J.Org.Chem. 51 (1986) 2034.
235
Y.Ishii, K.Suzuki, T.Ikariya, M.Saburi and S.Yoshikawa, J.Org.Chem. 51 (1986) 2822.
236
Y.Ishii, I.Sasaki, T.Ikariya, M.Saburi and S.Yoshikawa, Nippon Kagaku Kaishi (1985) 465; CA 104 (1986) 129208.
237
C.E.Castro, M.Jamin, W.Yokoyama and R.Wade, J.Am.Chem.Soc. 108 (1986) 4179.
238
C.-M.Che and W.M.Lee, J.C.S.Chem.Commun. (1986) 512.
239
A.Basu and K.R.Sharma, J.Mol.Catal. 38 (1986) 315.
240
M.Onishi, K.Hiraki, S.Kitamura and Y.Ohama, Nippon Kagaku Kaishi (1985) 400; CA 104 (1986) 108768.
241
D.Milstein, J.Mol.Catal. 36 (1986) 387.
242
H.Matsushita and S.Ishiguro, Agric.Biol.Chem. 49 (1985) 3071; CA 104 (1986) 68512.
243
Y.Ishii, T.Nakano, A.Inada, Y.Kishigami, K.Sakurai and M.Ogawa, J.Org.Chem. 51 (1986) 240.
244
P.Kvintovics, B.R.James and B.Heil, J.C.S.Chem.Commun. (1986) 1810.
528 245
35 (1986)
Catal. 246
C.Botteghi,
H.W.Krause
306
G.Delogu,
304
M.Graziani
J.Kaspar,
J.Organomet.Chem. 248
G.Chessa,
J.Organomet.Chem.
R.Spogliarich,
and M.Valderrama,
J.Mol.
161.
G.Chelucci,
F.Soccolini, 247
M.Martinez
I.Carkovic,
R.Sariego,
(1986)
and A.K.Bhatnagar,
S.Gladiali
and
(1986) 217. and F.Morandini,
407. J.Organomet.Chem.
302
(1986)
265. 249
M.J.Fernandez,
M.A.Esteruelas,
J.Organomet.Chem. 250
S.I.Hommeltoft, 108
251
(1986)
J.L.Atwood
G.A.Molander
253
G.A.Molander, (1986)
(1986)
E.W.Colvin
256
FArena,
J.G.Abdo
25 (1986)
A.Sera,
J.Am.Chem.Soc.
Inorg.Chem.
25
51 (1986)
and G.Hahn,
2596.
J.Org.Chem.
51
Anal.Biochem.
J.C.S.Chem.Commun.
A.Chiesi-Villa
154
(1986)
and C.Guastini,
1084. Inorg.
4589. T.Yoneda
697; CA 105 (1986)
K.Behari (1986)
and C.Hamilton, (1986) 221619.
S.Fukumoto,
R.S.Varma,
M.Varma
and H. Yamada,
24
225912.
and G.W.Kabalka,
(1986)
Heterocycles
Synth.Commun.
15 (1985)
190560.
and M.Gautam,
Oxid.Commun.
8 (1985j
237; CA 105
133169.
260
H.Alper
261
E.W.Colvin
262
H.Inoue
263
Y.Fort, (1986)
J.Org.Chem.
Belle
and S.Cameron,
1325; CA 105 259
B.E.La
C.Floriani,
(1986) 258
and R.Eisenberg,
and G.D.Stucky,
and G.Hahn,
559; CA 104
255
257
and L.A.Oro,
5259.
H.A.Akers,
Chem.
D.H.Berry
M.Covarrubias 343.
98.
252
254
(1986)
5345.
D.R.Corbin, (1986)
316
and F.Sibtain,
J.Organomet.Chem.
and S.Cameron,
and T.Nagata, R.Vanderesse 5487.
285
J.C.S.Chem.Commun.
J.C.S.Chem.Commun. and P.Caubere,
(1985)
225.
(1986)
1642.
(1986)
Tetrahedron
1177. Lett.
27
529
264
R.Vanderesse, Lett.
265
M.Lourak,
27 (1986)
Y.Fort
and P.Caubere,
Tetrahedron
5483.
J.Lu and Y.Qian,
Wuji
Huaxue
1 (1985)
130; CA 105
(1986)
190318. 266
Z.Zhang,
X.Liu
and Y.Fan,
30 (1985)
1351;
267
M.Kijima,
Y.Nambu
268
J.O.Osby,
S.W.Heinzman
(1986) 269
270
J.A.Cowan,
271
T.Tsuda,
(1985)
1851.
J.Am.Chem.Soc.
108
H.Toi,
and H.Ogoshi,
943.
Lett.
H.Satomi,
A.-M.Zigna
27 (1986)
1205.
T.Kawamoto
and T.Sageusa,
537.
and G.Balavoine,
J.Organomet.Chem.
306
Y.T.Xian
and G.Balavoine,
J.Organomet.Chem.
306
267. J.G.March
E.Amat,
275
O.A.Karpeiskaya, SSSR, Ser.Khim.
277
Lang.Ed.)
257.
F.Guibe,
T.Tabuchi, (1986)
T.Watanabe,
51 (1986)
274
276
Chem.Lett.
and B.Ganem,
(1986)
T.Hayashi,
F.Guibe,
(1986)
108
Tetrahedron
J.Org.Chem.
273
(Foreign
17047.
and T.Endo,
T.Fujisawa,
Y.Aoyama,
(1986)
(1986)
Tongbao
67.
J.Am.Chem.Soc.
272
CA 105
Kexue
and F.Grases, A.A.Belyi
(1985)
J.Inanaga
J.Mol.Catal.
35 (1986)
and M.E.Vol'pin,
1693; CA 104
(1986)
and M.Yamaguchi,
1.
Izv.Akad.Nauk. 148247.
Tetrahedron
Lett.
27
5237.
M.N.Bakola-Christianopoulou,
J.Organomet.Chem.
308
(1986)
C24. 278
E.Keinan
and N.Greenspoon,
279
A.Karim,
A.Mortreux
(1986) 280
281
and F.Pettit,
108
Tetrahedron
(1986) Lett.
27
K.Ishihara
and H.Yamamoto,
Tetrahedron
Lett.
27
987.
H.Brunner,
R.Becker
and S.Gauder,
Organometallics
739. 282
7314.
345.
A.Mori, (1986)
J.Am.Chem.Soc.
H.Brunner
and M.Kunz,
Chem.Ber.
119
(1986)
2868.
5 (1986)
530 283 284
S.Zehani
and G.Gelbard,
I.Shimizu,
M.Oshima,
J.C.S.Chem.Commun.
M.Nisar
(1985)
and J.Tsuji,
1162.
Chem.Lett.
(1986)
1775. 285
J.Tsuji,
T.Sugiura,
Commun.
(1986)
286
B.T.Khai
287
K.Yanada, (1986)
T.Okano, (1986)
J.Organomet.Chem.
and M.Hirobe,
and H.Alper,
Y.Moriyama,
309 (1986)
Tetrahedron
Lett.
C63.
27
J.Mol.Catal.
H.Konishi
and J.Kiji,
37 (1986)
359.
Chem.Lett.
1463. M.Iwahara
T.Okano, I.Pri-Bar
and T.Suzuki,
and O.Buchman, P.G.Ciattini,
S.Cacchi, Lett.
293
T.Nagano
I.Pri-Bar
289
292
J.C.S.Chem.
5113.
J.Blum,
291
and I.Minami,
922.
and A.Arcelli,
288
290
M.Yuhara
27 (1986)
51 (1986)
J.Org.Chem. E.Morera
(1986)
and G.Ortar,
1467.
734.
Tetrahedron
5541.
K.Tanaka
S.Kuwabata,
Chem.Lett.
and T.Tanaka,
Inorg.Chem.
25 (1986)
1691. 294
Z-Wang,
295
R.Fujiwara
7 (1986)
A.Kirsch-de
119
K.Kasuga,
H.Atarashi,
299
M.Trifan,
V.Marin
A.M.Syroezhko, Uchebn.Zaved., (1986) 301
301
Xuebao
44 (1986)
Y.Rollin
(1986)
and K.Kusuda, (1986)
D.Maetens
(1985)
298
278; CA 105
Huaxue
J.-C.Folest,
225; CA 104
Mesmaeker,
Acta.Chim.Hung.
(1986)
and Q.Zha,
199030.
J.Organomet.Chem.
H.Yamaguchi, Commun.
297
(1986)
S.Pellegrini,
S.Mabrouk, J.Perichon,
296
Z.Deng
C.Li,
863; CA 105
225978.
and R.Nasielski-Hinkens,
Chem.Lett.
(1986)
Makromcl.Chem.,Rapid
245; CA 104
and R.Avram,
and
391.
(1986) 139178.
(1986) 1679. Rev.Chim.(Bucharest)
37
99497.
A.A.Vikhorev,
and A.S.Yakovlev,
Khim.Khim.Tekhnol.
29 (1986)
Izv.Vyssh.
103;
CA 105
96861.
G.Balavoine, H.Rivi&e,
D.H.R.Barton, Tetrahedron
J.Bolvin,
Lett.
27.
A.Gref,
(1986)
2849.
N.Ozbalik
and
531
302
and T.M.Mal'kovskaya,
304
CA 104
A.Nishinaga,
(Decker) 306
307 308
G.Read
and M.Urgelles, (1986)
C.Martin,
M.Faraj,
and P.Dizabo,
309
K.Takehira,
310
V.P.Zagorodnikov,
312
E.Keinan,
Chem.Ind.
129119.
Trans.
J.Mol.Catal.
(1985)
and H.Orita,
M.N.Vargaftik,
(1986)
1591;
63.
J.Mercier,
37 (1986)
201.
Chem.Lett.
D.I.Kochubei,
Izv.Akad.Nauk
(1985)
1835.
A.L.Chuvilin,
SSSR,
Ser.Khim.
160974.
J.C.S.Chem.Commun.
K.K.Seth
37 (1986)
J.-M.Bregault,
J.Mol.Catal.
and M.A.Maifat,
253; CA 104
B.L.Feringa,
and T.Matsuura,
and D.M.M.Rohe, (1986)
J.C.S.Dalton
J.Martin,
T.Hayakawa
311
58 (1985)
5373.
J.Fillaux
(1986)
N.Pingel
and M.Bressan,
S.G.Sakharov
R.Sh.Latipov
Y.Toyoda
T.Shimizu,
309; CA 104
CA 104
A.Morvillo
N.M.Lebedeva,
2257.
W.Brijoux,
22 (1985)
and
108820.
51 (1986)
H.Bbnnemann,
N.Ozbalik
1727.
Zh.Prikl.Khim.(Leningrad)
H.Iwasaki,
J.Org.Chem. 305
(1986)
A.Gref,
(1986)
I.M.Kuznetswa,
R.A.Galimov,
2491;
J.Boivin,
J.C.S.Chem.Commun.
H.Rivibre, 303
D.H.R.Barton,
G.Balavoine,
(1986)
and R.Lamed,
909.
J.Am.Chem.Soc.
108
(1986)
3474. 313
M.Tanaka, (1986)
314
and T.Fuchikami,
K.Januszkiewicz
H.A.Zahalka, (1986)
315
H.Urata
Tetrahedron
Lett.
27
3165. and H.Alper,
J.Mol.Catal.
35
249.
S.Shinoda,
Y.Koie
and Y.Saito,
Bull.Chem.Soc.Jpn.
59 (1986)
2938. 316
W-Adam, (1986)
317
and E.Staab,
Tetrahedron
Lett.
27
2839.
S.E.Creager, (1986)
318
A.Griesbeck
S.A.Raybuck
and R.W.Murray,
J.Am.Chem.Soc.
4225.
I.Tabushi
and M.Kodera,
J.Am.Chem.Soc.
108
(1986)
1101.
108
532
319
M.K.Dickson
P.K.Wong, (1985)
320
I.Tabushi
321
P.J.Martinez Arias
and K.Morimitsu,
J.C.S.Chem.Commun.
(1986)
L.M.Stock,
Tetrahedron
de la Cuesta,
and F.Delgado
CA 105 322
and L.L.Sterna,
1565.
E.Rus
Lett.
Martinez,
27 (1986)
51.
J.M.Blasco
Bayo, An.Quim.,Ser.A
81 (1985)
414;
152354.
and S.H.Wang,
Fuel
64 (1985)
1713;
CA 104
(1986)
53267. 323
G.D.Tkacheva CA 104
324
(1986)
105
- Kochi (1986)
Kogyo
T.P.Kenigsberg,
327
329
28
Koto
Senmon
N.G.Ariko,
and A.Kurokawa, Gakko
23 (1985)
(1985)
(1985)
N.I.Mitskevich
1485;
27; CA 104
1289;
Gakujutsu 111; CA
G.R.Steinmetz
and C.E.Sumner,
CA 105
208316.
129276. Proc.Conf.Coord.Chem.
175255. J.Catal.
Neftekhimiya
F.F.Shcherbina,
5974.
Neftepererab.Neftekhim.
(1986)
(1986)
and V.F.Nazinok,
(1986)
and K.B.Yatsimirskii,
89; CA 104
(1986)
CA 105
and D.N.Tmenov,
Yu.I.Bratushko, 10th
328
T.Kubokawa
26 (1936)
F.V.Shcherbina (Kiev)
21 (1985)
8299.
Kinet.Katal. 326
Zh.Org.Khim.
129590.
M.Shigeyasu,N.Osaki, Kiyo
325
and B.V.Suvorov,
26 (1986)
100
(1986)
549;
409; CA 105 (1986)
225587. 330
A.M.Ivanov CA 104
331
A.M.Ivanov, (1986)
332 333
S.Lundk,
335
and E.V.Shuran,
M.Vaskovh,
34 (1986)
(1985)
N.P.Belous,
1078;
Ukr.Khim.Zh.(Russ.Ed.)
52
133172. J.0rg.Chem.51
P.Lederer
I.V.Zakharov
(1986)
and J.Veprek-Siska,
and P.E.Strizhak,
(1986)
L.K.D'yachek,
(1986)
26 (1985)
1365. J.Mol.
321.
852; CA 104
F.F.Shcherbina, CA 104
(1986)
and H.-C.Szabo,
Yu.V.Geletii, 26
Kinet.Katal.
148087.
372; CA 105
R.DiCosimo
Catal. 334
and E.V.Shuran,
(1986)
N.N.Kalibabchuk,
Ukr.Khim.Zh.(Russ.Ed.) 156515.
Kinet.Katal.
68363. D.N.Tmenov
52 (1986)
100;
and
533 336
A.L.Mosolova CA 105
337
A.B.Goel, 117
25 (1985)
540;
42411.
P.E.Throckmorton
and R.A.Grimm,
Inorg.Chim.Acta
(1986) L15.
338
A.B.Goel,
339
J.van
Inorg.Chim.Acta
Gent,
Bekkum, 340
Neftekhimiya
and A.L.Matienko,
(1986)
S.Hata,
Lett.
S.Ito
(1986) Lll.
A.W.P.G.Peters
A.A.Wismeijer,
Tetrahedron
A.Kunai,
121
27 (1986)
Rit and H.van
1059.
and K.Sasaki,
J.Org.Chem.
51 (1986)
3471. 341
L.Gasella
and L.Rigoni,
342
V.P.Morozov
and T.N.Grishko,
Khim.Tekhnol. 343
K.Nomiya, CA 105
344
(1986)
H.C.Bajaj (1985)
346
1669.
Izv.Vysh.Uchebn.Zaved.,Khim. 31; CA 104
and M.Miwa,
T.Miyazaki
CA 105
(1986)
(1986)
Polyhedron
68352. 5 (1986)
1031;
and M.M.Taqui
and M.Miwa,
Polyhedron
5
69944.
Khan,
339; CA 104 (1986)
M.M.Taqui
(1985)
85754.
Y.Sugie,
(1986) 1267; 345
28 (1985)(5)
H.Murasaki
K.Nomiya,
J.C.S.Chem.Comunun.
React.Kinet.Catal.Lett.
28
148077.
Khan and A.Prakash
Rao, J.Mol.Catal.
35 (1986)
237. 347
M.A.Beckett
and R.B.Homer,
Inorg.Chim.Acta
118
(1986)
Lll. 348
N.N.Tsekhina 59 (1986)
and B.G.Freidlin,
628; CA 105
(1986)
Zh.Prikl.Khim.
(Leningrad)
42115.
349
M.A.Beckett
and R.B.Homer,
Inorg.Chim.Acta
115
(1986) L25.
350
M.A.Beckett
and R.B.Homer,
Inorg.Chim.Acta
122
(1986) L5.
351
V.P.Zagorodnikov
and M.N.Vargaftik,
Ser.Khim.
2652.
352
(1985)
S.Kitagawa, bu Kenkyu
353
M.Munakata Hokoku
N.Kitajima,
354
M.E.Cass
(1985)(21)
K.Whang,
J.C.S.Chem.Commun.
and M.Ohmae,
and C.G.Pierpont,
SSSR,
Kinki
Rikogaku-
83; CA 104
Y.Moro-oka, (1986)
Izv.Akad.Nauk
Daigaku
(1986)
A.Uchida,
224421.
and Y.Sasada,
1504. Inorg.Chem.
25 (1986) 122.
534 355
T.Funabiki,
S.Tada,
T.Yoshioka,
J.C.S.Chem.Commun. 356
357
F.Funabiki,
A.Mizoguchi,
H.Sakamoto
and S.Yoshida,
U.Russo,
M.Vidali,
Inorg.Chim.Acta 358
(1986)
S.Tsuruya,
T.Sugimoto,
and S.Yoshida,
S.Tada,
J.Am.Chem.Soc.
B.Zarli,
120
M.Takano
1699.
R.Furello
M.Tsuji,
108
(1986)
2921.
and G.Maccarrone,
(1986) Lll.
S.-I.Yani
and M.Masai,
Inorg.Chem.
25 (1986)
1072.
141,
536 389
K.Kasuga, CA 105
390
R.B.Homer, (1985)
391
T.Oishi
(1986)
Y.Liu,
R.D.Cannon,
115; CA 104 K.Wang,
Ziran
and Y.Yamamoto,
Polyhedron
5 (1986)
883;
90090.
X.Sun,
Kexueban
S.S.B.Kim,
(1986)
X.Zhu
15 (1985)
392
S.-M.Peng
393
G.Speier
394
E.Balogh-Hergovits
Bull.Korean.Chem.Soc.
and H.Li,
Xibei
(3) 47; CA 104
Inorg.Chim.Acta
and D.-S.Liaw, and L.Parkanyi,
6
50446.
J.Org.Chem.
and G.Speier,
Daxue
(1986)
113
Xuebao,
179064.
(1986)
51 (1986)
J.Mol.Catal.
Lll.
218. 37 (1986)
309. 395
M.M.Al-Arab
and G.A.Hamilton,
J.Am.Chem.Soc.
108 (1986)
5972. 396
I.Ondrejkovicova 10th
397
(1985)
M.M.Taqui
and G.Ondrejovic,
251; CA 104 (1986)
Khan,
Proc.Conf.Coord.Chem.
236144. A.Hussain
M.R.H.Siddiqui,
and M.A.Moiz,
Inorg.Chem.
25 (1986)
398
K.Yamamoto,
Polyhedron
399
D.P.Riley
and J.D.Oliver,
Inorg.Chem.
400
D.P.Riley
and P.E.Correa,
J.C.S.Chem.Commun.
401
A.A.Andreev
403
M.Hronec
(1986)
and L.Malik,
O.Gombosuren, Univ.,Ser.2:
404
5 (1986)
and K.Tashkova,
(4) 59; CA 105 402
2765.
25 (1986)
90148.
1814.
(1986)
Dokl.Bolg.Akad.Nauk
J.Mol.Catal.
26 (1985)
M.A.Ismailova,
Kh.M.Yakubov,
A.N.Astanina,
Zh.Obshch.Khim.
60920.
(1986)
1097.
39 (1986)
63336.
V.V.Berentsveig Khim.
913; CA 105
35 (1986)
169.
and A.P.Rudenko, 588; CA 104
E.Ya.Offengenden 56 (1986)
Vest.Mosk.
(1986)
40544.
and
527; CA 105
(1986)
537 407
R.Rajaram
K.Vijayasri, 117
(1986)
Huaxue
Xuebao
408
W.Chen,
409
J.Muzart,Tetrahedron
410
J.P.Collman, 108
411
(1986)
(1986) 413
414
416
A.Kunai,
(1986)
418
S.Hata,
420
421
CA 104
S.Ito
and K.Sasaki,
108
J.Mol.Catal.
36
J.Am.Chem.Soc.
108
and S.M.Hecht,
J.Am.Chem.
7839. Chem.Soc.
V.M.Derkacheva,
(1986)
6 (1985)
I.A.Zheltukhin,
and E.A.Luk'yanets,
(3) 138;
O.L.Kaliya,
Zh.Org.Chim.
21 (1985)
185790.
C.D.Stucky
and C.A.Tolman,
E.A.Wahab,
Egypt.J.Chem.
J.C.S.Chem.Commun.
27 (1984) 81; CA 104
E.Kotani,
S.Kobayashi,
33 (1985)
H.Orita,
4680;
T.Hayakawa
Y.Ishii CA 105
and S.Tobinaga, (1986)
and K.Takehira,
Chem.Pharm.
78558. Bull.Chem.Soc.Jpn.
59
2637.
Y.Sasson,
S.C.Pati,
G.D.Zappi
and R.Neumann,
H.P.Pathy
and B.R.Dev,
J.Org.Chem.
51 (1986)
~ Proc.Indian
Part A 51 (1985) 853; CA 105 (1986) 423
J.Am.Chem.Soc.
185801.
2880. 422
J.C.S.
1521.
I.Ahmed,
(1986)
and D.Mansuy,
and J.K.Kochi,
R.L.Mutholland,
(1986)
N.Herron,
Bull.
J.Am.Chem.Soc.
6012.
S.V.Barkanova,
(1986) 419
J.F.Bartoli
J.Suh and K.Nahm, Bull.Korean CA 104 (1986) 129277.
(1986)
3139.
and K.S.Suslick,
S.Perrier
V.N.Kopranenkov
417
5968.
341.
T.J.Reinert
D.C.Heimbrook,
2018;
(1986)
297.
Sot. 108 415
27 (1986)
and J.I.Braumann,
J.-P.Renaud,
K.Srinivasan,
(1986)
Lett.
891; CA 105
7281.
(1986) 413a
43 (1985)
T.Kodadek
P.Battioni,
B.R.Cook,
Inorg.Chim.Acta
2588.
Chem.Commun. 412
and J.C.Kuriacose,
133.
N.I.Kuznetsova, Yu.I.Yermakov,
M.A.Fedotov, J.Mol.Catal.
Natl.Sci.Acad.,
152387.
V.A.Likholobov 38 (1986)
263.
and
538 424
S.Yamaguchi, (1986)
425
S.Yamaguchi, (1986)
426
and S.Enomoto,
Bull.Chem.Soc.Jpn.
M.Inoue
and S.Enomoto,
Chem.Pharm.Bull.
445; CA 105 (1986)
L.A.Deardurff, 51 (1986)
427
M.Inoue
59
2881. 34
208291.
M.S.Alnajjar
and D.M.Camaioni,
J.Org.Chem.
3686.
A.L.J.Beckwith
and A.A.Zavistas,
J.Am.Chem.Soc.
108
(1986)
8230. 428
E.V.Dehmlov CA 104
429
and J.K.Makrandi,
(1986)
J.M.Klunder, (1986)
J.Chem.Res.Synop.
(1986)
32;
185804. S.Y.Ko
and K.B.Sharpless,
J.Org.Chem.
51
3710.
430
R.M.Hanson
and K.B.Sharpless,
J.Org.Chem.
51 (1986)
1922.
431
J.G.Millar
and E.W.Underhill,
J.Org.Chem.
51 (1986)
4726.
432
H.J.Gordon, Synth.
433
Y.Kitano, Commun.
434
K.B.Sharpless,
63 (1985)
T.Matsumoto, (1986)
C.Puchot,
O.Samuel,
S.Hatakayama, (1985)
R.E.Babine,
437
M.Kawai,
440
K.Sakurai
S.Zhao,
Lett.
C.Agami
and H.B.Kagan,
J.C.S.Chem.Commun.
27 (1986)
and D.H.Rich,
R.Lazaro, Lett.
Y.Honda,
A.Ori,
R.Barret,
5791.
Tetrahedron
Lett.
27
H.Ranieriseheno
and P.Viallefont,
27 (1986) 4735.
and G.Tsuchihashi,
F.Pautet,
M.Daudon
Chem.Lett.
and B.Mathian,
(1986)
1417.
Bull.Soc.Chim,
94 (1985) 439; CA 104 (1986) 88158.
P.Mosset,
(1985)
J.C.S.Chem.
2353.
and S.Takano,
Tetrahedron
Tetrahedron
W.Xiao,
and F.Sato,
1877.
Tetrahedron 442
(1986)
R.Jacquier,
Belg. 441
E.Dunach,
108
J.H.Gardner
(1986)
439
Org.
1759.
436
438
Y.Takeda
and R.Regenye, 88368.
1732.
J.Am.Chem.Soc. 435
C.M.Exon
66; CA 104 (1968)
P.Yadagiri, Lett.
Y.Gong,
S.Lumin,
27 (1986)
C.Feng,
364; CA 105
Z.Wang
(1986)
J.Capdevilla
and J.R.Falck,
6035. and W.Xu,
133147.
Cuihua
Xuebao
6
539 443
444
P.J.Martinez
Minguez,
181; CA 104
(1986) 7460.
P.J.Martinez Medina, (1986)
445
X.Ye,
S.Qu
Aceites
Aceites
and
(Seville)
E.Rus Martinez
(Seville)
36 (1985)
and A.Justicia
36 (1985)
177; CA 104
and Y.Wu,
Huaxue
Xuebao
43 (1985)
572; CA 104
19254.
Y.Kurusu, (1986)
447
de la Cuesta,
Grasas
E.Rus Martinez
Grasas
7459.
(1986) 446
de la Cuesta,
L.M.Cotoruelo
Y.Masuyama,
M.Saito
and S.Saito,
J.Mol.Catal.
37
235.
J.Prandi,
H.B.Kagan
(1986)
2617.
448
D.Prat
and R.Lett,
449
D.Prat,
B.Delpech
and H.Mimoun,
Tetrahedron and R.Lett,
Tetrahedron
Lett.
Lett.
27 (1986)
Tetrahedron
27
707.
Lett.
27 (1986)
711. 450
C.L.Hill
and R.B.Brown,
451
R.J.M.Nolte, Sot. 108
452
B.De
453
J.A.S.J.Razenberg,
S.Takagi, (1986)
455
and B.Meunier,
(1986)
(1986)
and R.Schuurman,
536. J.Am.Chem.
J.C.S.Perkin
Trans.11.
(1985)
42569. R.J.M.Nolte
and W.Drenth,
J.C.S.Chem.
277.
T.K.Miyamoto
and Y.Sasaki,
Bull.Chem.Soc.Jpn.
59
2371.
K.Srinivasan, (1986)
108
2751.
CA 104 (1986)
Commun. 454
J.A.S.J.Ranzenberg
(1986)
Poorter
1735;
J.Am.Chem.Soc.
P.Michaud
and J.K.Kochi,
J.Am.Chem.Soc.
108
2309.
456
C.-M.Che,
457
Y.Tatsuno,
W.-K.Cheng, A.Sekiya,
J.C.S.Chem.Commun. K.Tani
and T.Saito,
(1986)
1443.
Chem.Lett
(1986)
889. 458
T.C.Woon, (1986)
459
460
L.Devocelle,
9 (1985)
J.P.Collman, 108
and T.C.Bruice,
J.Am.Chem.Soc.
108
7990.
D.Mansuy, Chim.
C.M.Dicken
(1986)
I.Artaud
711; CA 104
P.D.Hampton 7861.
and J.P.Battioni,
(1986)
Nouv.J.
144570.
and J.I.Brauman,
J.Am.Chem.Soc.
461
T.C.Woon
C.M.Dicken, (1986)
and T.C.Bruice,
J.Am.Chem.Soc.
108
1636.
462
J.T.Croves
463
S.Takagi,
and Y.Watanabe, E.Takahashi
J.Am.Chem.Soc.
and T.K.Miyamoto,
108
(1986)
Chem.Lett.
507.
(1986)
1275. 464
T.G.Traylor, D.Dolphin,
465
108
Y.Iamamoto
P.S.Traylor
(1986)
and
2783.
and T.Nakano,
J.Am.Chem.Soc.
108
3529. J.Umehara,
T.Muto,
F.C.Bradley
B.P.Murch,
T.Miura
H.Masumori,
33 (1985) 4749;
Pharm.Bull. 467
B.E.Dunlap,
J.Am.Chem.Soc.
T.G.Traylor, (1986)
466
T.Nakano,
CA 105
and L.Que,
and M.Kimura,
(1986)
Chem.
134234.
J.Am.Chem.Soc.
108
(1986)
5027. 468
A.Kittaka,
Y.Sugano, H.Umezawa,
469
M.Otsuka,
Tetrahedron
J.C.DObsOn,
W.K.Seok
Lett.
M.Ohno,
Y.Sugiura
27 (1986)
and T.J.Meyer,
and
3635.
Inorg.Chem.
25 (1986)
1513. 470
C.-M.Che
and W.C.Chung,
471
C.M.Che,
W.K.Cheng
J.C.S.Chem.Commun.
and T.C.W.Mak,
(1986)
386.
J.C.S.Chem.Commun.
(1986)
200. 472
A.F.Tai, 108
473
L.D.Margerum
(1986)
V.I.Korenskii, V.L.Volkov, Khim.
474
475
V.D.Skobeleva,
G.S.Zakharova
55 (1985)
1969;
J.R.L.Smith,
D.I.Richards, Trans.
O.Bortolini,
V.Conte,
(1986)
C.B.Thomas
II (1985) F.Di
I.P.Kolenko, Zh.Obshch.
87965. and W.Whittacker,
1677; CA 104
Furia
L.G.Shevchuk,
and V.G.Kul'nevich,
477
V.G.Kharchuk,
(1986)
and C.Modena,
108i308.
J.Org.Chem.
2661.
S.P.Gavrilova,
(1986)
J.Am.Chem.Soc.
and V.N.Vinogradova,
CA 104
J.C.S.Perkin
51 (1986) 476
and J.S.Valentine,
5006.
L.A.Badovskaya,
Kinet.Catal.
26 (1985)
N.A.Vysotskaya 1248; CA 104
50460.
C.Venturello
and M.Ricci,
J.Org.Chem.
51 (1986)
1599.
541
478
479
M.Lj.Mihailovic, Tetrahedron
Lett.
M.B.Booking
and D.J.Intihar,
Chem.Technol. 480
N.Goto Kiyo,
481
35A
485
486
(1986)
488
Koto
Senmon
57; CA 105 (1986)
A.Kajiwara
H.Tomioka,
59 (1986)
J.Jagannadham,
Gakko
42406.
J.Am.Chem.Soc.
a (1985)
108
and H.Nozaki,
B.Sethuram
41; CA 105
J.Rajaram
Bull.Chem.
and N.T.Rao,
(1986)
Curr.Sci.
54
133378.
and K.S.Tripathy, 1; CA 104 (1986)
E.J.Smith,
Oxid.
208277.
and J.C.Kuriacose,
(1986)
P.S.Radhakrishnamurti
Trans.
J.C.S.
105.
1279; CA 105
J.A.Cabeza,
and A.Nakamura,
K.Oshima
M.A.Rao,
K.Vijayashri,
Dalton
Kogyo
96830.
434.
Sci., Sect A 5 (1985) 487
Niihama
and T.C.Bruice,
T.Sugawara,
S.Kanemoto,
(1985)
J.Chem.Technol.Biotechnol.,
365; CA 105 (1986)
5495.
N.Ueyama,
Commun.
and R.Vukicevic,
2287.
21 (1985)
P.N.Balasubramanian
Soc.Jpn. 484
(1985)
and M.Kidawara,
Chem.Commun. 483
27 (1986)
Rikogaku-hen
(1986) 482
S.Konstantinovic
H.Adams
Indian
J.Phys.Nat.
87950.
and P.M.Maitlis,
J.C.S.
(1986) 1155.
H.Hingorani,
H.C.Goyal,
Rev.Roum.Chim.
G.Chandra
30 (1985)
489
R.B.Ganunill and S.A.Nash,
490
S.J.Danishefsky
and S.N.Shrivastava,
725; CA 104 (1986) J.Org.Chem.
and M.P.DeNinno,
148081.
51 (1986)
3116.
J.Org.Chem.
51 (1986)
Tetrahedron
41 (1985)
2615. 491
492
H.Nagashima,
K.Sato
and J.Tsuji,
5645: CA 105
(1986)
171451.
B.M.Choudary
and M.Lakshmi
Kantam,
J.Mol.Catal.
36 (1986)
343. 493
S.C.Goyal
and L.K.Saxena,
554; CA 104 494
P.Smith (1986)
(1986)
and K.R.Maples, 152435.
J.Indian
Chem.Soc.
62 (1985)
185802. J.Magn.Reson.
65 (1985)
491; CA 105
495
R.Barret, (1985)
496
728; CA 104 (1986;
D.G.Batyr,
497
Mold.SSSR,
(1986)
D.G.Batyr,
498
B.Pispisa CA 104
499
(1985) 500
!1985)
(5) 52;
and Yu.Ya.Kharitonov,
435; CA 105 (1986)
78338.
Macromolecules
19 (1986)
S.Hansson
E.Amat
and C.Moberg,
(1986)
Acta
and J.G.March,
Bull.Soc.Chim.Fr.
501
K.Nakamija,
M.Kojima
and J.Fujita,
Chem.Lett.
502
E.W.Harlan,
J.M.Berg
and R.H.Holm,
J.Am.Chem.Soc.
504
O.Bortolini,
505
W.Ando
506
T.Takata
508
1483.
108
108
Lett.
Tetrahedron T.Takata
27 (1986)
Lett.
27 (1986)
and S.Oae,
3391. 1591.
Tetrahedron
581.
C.Frechou
and G.Demailly,
Tetrahedron
Lett.
2867.
P.Ferraboschi,
M.N.Azadani
and E.Santaniello,
43; CA 105 (1986)
510
H.Kang
and J.L.Beauchamp,
511
P.S.R.Murti,
H.P.Panda
227; CA 105
J.W.Suggs
and M.Rossi,
6257.
Tetrahedron
S.Fujiwara,
27 (1986)
16 (1986)
512
(1986)
J.Am.Chem.Soc.
G.Modena
G.Licini,
27 (1986)
and W.Ando,
G.Solladie,
(1985)
and R.H.Holm,
F.Di Furia,
and L.Huang,
27 (1986) 509
E.W.Harlan
Lett.
K.Fujimori, Lett.
42083.
7856.
Tetrahedron
507
(1985)
6992.
J.P.Caradonna, (1986)
B39
185949.
(1986)
503
904;
Chem.Scand.
594; CA 105
(1986)
Izv.
130236.
593; CA 104
F.Grases,
and S.V.Kil'mininov,
A.A.Kirienko
and A.Palleschi,
T.Antonsson,
40
129324.
Ser.Biol.Khim.Nauk
12 (1986)
(1986)
Pharmazie
75886.
V.G.Isak,
Koord.Khim.
and M.Daudon,
A.A.Kirienko
V.G.Isak,
Akad.Nauk CA 104
B.Mathian
F.Pautet,
and L.Ytuarte,
J.Am.Chem.Soc.
and D.C.Pradhan,
(1986)
Synth.Commun.
152219. 108
(1986)
Oxid.Commun.
5663. 8
208296. Tetrahedron
Lett.
27 (1986)
437.
543
513
B.Bhattacharjee, M.N.Bhattacharjee, M.Bhattacharjee and A.K.Bhattacharjee, Bull.Chem.Soc.Jpn. 59 (1986) 3217.
514
515
R.Gulge, and A.M.Shaligram, Indian J.Chem. 24B (1985) 815; CA 105 (1986) 172757. F.P.Ballistreri, S.Failla, G.A.Tomaselli and R.Curci, Tetrahedron Lett. 27 i1986) 5139.
516
F.Freeman and J.C.Kappos, J.Org.Chem. 51 (1986) 1654.
517
I.H.Al-Wahaib, B.S.Razouki and B.S.Abdul-Aziz, J.Pet.Res. 5 (1986) 55; CA 105 (1986) 193297.
518
P.Viski, Z.Szeverenyi and L.Simdndi, J.Org.Chem. 51 (1986) 3213.
519
P.Guiton, S.Menager and O.Lafont, Ann.Pharm.Fr. 43 (1985) 373; CA 105 (1986) 5998.
520 521
T.Ogino, T.Kazama and T.Kobayashi, Chem.Lett. (1985) 1863. J.F.Perez-Benito and D.G.Lee, Can.J.Chem. 63 (1985) 3545; CA 104 (1986) 19269.
522
D.G.Lee, K.C.Brown and H.Karaman, Can.J.Chem. 64 (1986) 1054; CA 105 (1986) 190337.
523
R.Rathore, P.S.Vankar and S.Chandrasekaran, Tetrahedron Lett. 27 (1986) 4079.
524
Y.Landais, A.Lebrun and J.P.Robin, Tetrahedron Lett. 27 (1986) 5377.
525
Y.Landais and J.-P.Robin, Tetrahedron Lett. 27 (1986) 1785.
526
E.Vedejs and C.M.McClure, J.Am.Chem.Soc. 108 (1986) 1094.
527
M.Tokles and J.K.Snyder, Tetrahedron Lett. 27 (1986) 3951.
528
T.Yamada and K.Narasaka, Chem.Lett. (1986) 131.
529
J.E.Rice, E.J.LaVoie, D.J.McCaustland, D.L.Fischer and J.C.Wiley, J.Org.Chem. 51 (1986) 2428.
530
Z.Cvengrosovh, M.Hronec, J.Kizlink, T.Pasternakova, S.Holotik and J.Ilavsky, J.Mol.Catal. 37 (1986) 349.
531
E.Baciocchi, A.Dalla Cort, L.Eberson, L.Mandolini and C.Rol, J.Org.Chem. 51 (1986) 4544.
532
T.Morimoto, M.Hirano and T.Koyama, J.C.S.Ferkin Trans.11 (1985) 1109; CA 104 (1986) 50452.
544 533
I.V.Kozhevnikov,
534
D.Dimitrov, (1984)
535
V.I.Kim,
Ser.Khim.
SSSR,
(1985)
V.Sirakova
399; CA 104
E.V.Gusevskaya,
536
(1986)
Izv.Akad.Nauk
(1986)
and R.Stefanova,
224419.
Oxid.Conunun.
7
88854.
I.E.Beck,
A.G.Stepanov,
Yu.I.Yermakov
V.M.Nekipelov, 37 (1986)
and E.P.Talzi,
2167; CA 104
V.A.Likholobov,
and K.I.Zamaraev,
J.Mol.Catal.
177.
J.-E.Backvall
and A.Heumann,
J.Am.Chem.Soc.
108
(1986)
7107. 537
J.Skarzewski
and J.Mlochowski,
963; CA 105 538
539
F.Casablanca,
Chim.Acta
113
H.Mimoun,
M.Mignard,
108
542
G.Amato,
A.Arcoria,
J.Mol.Catal.
37 (1986)
545
F.Di
35 (1986)
(1986) 546
547
548
Furia,
G.A.Tomaselli, and G.Valle,
F.Di
Furia
and
2374.
G.Modena
S.S.Gupta
1503; CA 104
J.C.S.Perkin
and G.A.Ayoko,
(1986)
M.P.Alvarez CA 105
129189.
and A.Schionato,
J.Mol.
and A.Banerjee,
J.C.S.Perkin
(1986) 87964. N.Chandrasekara,
K.Ramalingam
Trans.
1183; CA 104
II (1985)
5374.
M.A.Olatunji CA 105
and Y.Kita,
(1986)
G.Modena
G.A.Tomaselli,
51 (1986)
J.G.Lakshmanan,
and K.Selvaraj,
J.Am.Chem.
47.
S.Dey,
II (1985)
P.G.Arjunan,
Inorg.
165.
F.P.Ballisteri,
K.K.S.Gupta, Trans.
F.Di Furia,
J.Org.Chem.
O.Bortoloni,
Y.Tamura
2743; CA 104
F.P.Ballistreri,
V.Conte,
A.Arcoria,
and J.Fischer,
and L.Saussine,
M.Sakamoto,
33 (1985)
O.Bortolini,
Catal. 544
P.Brechot
T.Kawasaki,
G.Modena, 543
Y.Gauffreteau
3711.
Chem.Pharm.Bull. 541
(1985)
(1986) 173.
(1986)
C.S.Chien,
327
171921.
M.Postel,
Sot. 540
(1986)
J.Prakt.Chem.
Macho,
(1986)
V.Jagannadham, 8 (1985)
Bull.Soc.Chim.Fr.
(1985)
705;
22 (1985)
499;
171597. Acta Cient.Compostelana
23797. M.A.Rao,
31; CA 105
B.Sethuram
(1986)
96837.
and T.N.Rao,
Oxid.Commun.
545
549
M.Mazumdar,
G.Mishra, (India)
S.K.Laha
57 (1985) 187; CA 105
550
N.F.Magri
551
T.Brunelet,
and D.G.I.Kingston, C.Jouitteau
and R.Prasad, (1986)
J.Inst.Chem.
208432.
J.Org.Chem.
and G.Gelbard,
51 (1986)
J.Org.Chem.
797. 51
(1986) 4016. 552
553
15 (1985)
T.Brunelet CA 104 S.Kim
555
S.Czernecki,
557
559
R.Varadarajan
and R.K.Dhar, 153419.
(1986)
S.A.Vorskanyan,
M.S.Akhtar,
J.Org.Chem.
51
J.M.Antelo,
and H.Kim, F.Arce,
Chim.Ital.
115
R.Gurumurthy (1986)
1; CA 104
and M.Copalakrishnan,
565
R.W.Curley
566
A.Abiko,
(1986)
R.Bartzatt
474;
Arm.Khim
J.Heterocycl.Chem.
22
Lett.
27 (1986)
4889.
and A.Varela,
(1986)
Gazz.
129294.
Indian
J.Chem.
25A
208305. Bull.Assoc.Kinet.India
7(2)(1985)
14104.
and C.J.Ticoras, J.C.Roberts,
Lett.
(1986)
133680.
J.Franco
493; CA 104
and D.N.Shanna,
25A
and Sh.O.Badanyan,
Tetrahedron
(1986)
J.Chem.
152638.
A.Castro,
(1985)
476; CA 105
R.Simlot
Indian
(1986)
(1986)
and H.Christol,
1775.
and A.P.Bhaduri,
1323; CA 105
562
P.Morand
Zh.A.Chobanyan 424; CA 105
M.Seth
M.F.Schlecht
567
3297.
186768.
and G.Ville,
27 (1986)
CA 105
hedron
264;
and K.Vijayakumaran,
11; CA 104 (1986)
E.Torreilles, Lett.
561
564
59 (1986)
C.L.Stevens
K.Vijayakumaran
H.-J.Cristau,
(1985)
563
Bull.Chem.Soc.Jpn.
16 (1986)
Zh. 38 (1985) 560
(1985)
5472.
Tetrahedron 558
J.Chem.Res.,Synop.
C.Georgoulis,
Synth.Commun.
(1986)
Synth.
133714.
50453.
and D.C.Lhim,
S.Czernecki,
and C.Palomo,
1197; CA 105 (1986)
and G.Gelbard,
(1986)
554
556
F.P.Cossio
A.Gonzales,
C.Lopez, Commun.
27 (1986)
and J.Carr,
J.Org.Chem.
T.Takemasa
51 (1986)
and S.Masamune,
256. Tetra-
4537. Transition
Met.Chem.
11 (1986)
414.
568
569
K.S.Kim, 27 (1986)
2875.
Manibala,
P.K.Tandon
266 570
N.H.Lee
Y.H.Sonq,
(1985)
and B.Krishna,
1153; CA 104
M.E.Marmion
and C.S.Hahn,
Tetrahedron
Lett.
Z.Phys.Chem.(Leipziq)
(1986) 75900.
and K.J.Takeuchi,
J.Am.Chem.Soc.
108
(1986)
510. 571
L.Roecker
572
P.Kumar, 29
573
K.C.Gupta
(1985)
575 576
577
Bull.
579
CA 105 (1986)
2053.
(1986)
Zh.
80922.
J.C.S.Dalton
434; CA 105
(2) 92; CA 105
Trans.
105
and P.K.Tandon, (1986)
(1986)
(1986)
Orient.J.Chem.
208322,
and G.S.S.Murthy,
(1986)
J.Indian
96827.
and G.S.S.Murthy,
V.J.Jaqannadham
J.S.Thompson
87938.
and V.I.Kurlyankina,
B.Krishna
V.Jaqannadham
255; CA
(1986)
1145; CA 105
H.S.Sinqh,
T.R.Reddy,
607;
179144.
62 (1985)
8 (1985) 581
A.I.Buyanov
and D.H.Macartney,
T.R.Reddy,
26 (1985)
Natl.Acad.Sci.Lett.
59 (1986)
J.W.Herbert
2 (1986) 580
(4) 111; CA 104
56 (1986)
Chem.Soc.
React.Kinet.Catal.Lett.
and A.P.Sinqh,
Chem.Soc.Jpn.
L.G.Revel'skaya,
M.Manibala,
4066.
136716.
Kinet.Katal.
Obshch.Khim.
1931; 578
8 (1985)
M.Kohno,
108 (1986)
33701.
A.K.Singh
(India)
(1986)
and B.Krishna,
(1986)
B.Singh,
J.Am.Chem.Soc.
and K.Vehari,
297; CA 104
P.K.Tandon CA 104
574
and T.J.Meyer,
Oxid.Commun.
208298.
and J.C.Calabrese,
J.Am.Chem.Soc.
108
(1986)
1903. 582
J.Dzigiec,
583
N.K.Mohanty
Pol.J.Chem.
59 (1985) 731; CA 105
and R.K.Nanda,
Bull.Chem.Soc.Jpn.
(1986)
190329.
58 (1985)
3597. 584
H.Laatsch,
Liebigs
Ann.Chem.
(1986)
1655; CA 105
(1986)
225989. 585
M.Varma CA 104
and K.C.Nand, (1986)
51031.
React.Kinet.Catal.Lett.
27 (1985)
97;
547
586
R.D.Kharga and H.B.Mishra, J.Nepal.Chem.Soc. (1983) (3) 45; CA 104 (1986) 50448.
587
M.Uma and A.Manimekalai, Indian J.Chem.,Sect.B. 24B (1985) 1088; CA 105 (1986) 23800.
588
J.-M.Melot, F.Texier-Boullet
and A.Foucaud, Tetrahedron
Lett. 27 (1986) 493. 589
C.S.Chien,
T.Takanami, T.Kawasaki and M.Sakamoto, Chem.
Pharm.Bull. 33 (1985) 1843; CA 104 (1986) 109407. 590
P.V.Sreenivasulu, M.Adinarayana, B.Sethuram and T.N.Rao, Oxid.Ccmunun. 8 (1985) 199; CA 105 (1986) 190262.
591
R.Iqbal and F.Malik, J.Chem.Soc.Pak. 8 (1986) 83; CA 105 (1986) 226295.
592
F.Mata-Perez and J.Perez-Benito, Acta Cient.Compostelana 22 (1985) 563; CA 104 (1986) 224422.
593
F.Mata-Perez and J.Perez-Benito, Z.Phys.Chem. Leipzig (1986) 120; CA (1986) 136609.
594
M.A.El-Dessouky and N.M.El-Mallah, Bull.Soc.Chim.Fr.
267
(1985)
163; CA 104 (1986) 19249. 595
P.V.S.Rao, G.V.Saradamba and K.Ramakrishna, Indian J.Chem. 24A (1986) 438; CA 104 (1986) 185781.
596
N.Nath and L.P.Singh, Rev.Roum.Khim. 31 (1986) 489; CA 105 (1986) 85792.
597
A.A.Awashti and S.K.Upadhyay, Indian J.Chem. 25A (1986) 292; CA 105 (1986) 5868.
598
J.W.Bunting and D.Stefanidis, J.Org.Chem. 51 (1986) 2060.
599
J.W.Bunting and D.Stefanidis, J.Org.Chem. 51 (1986) 2068.
600
S.Yoshifuji, Y.Arakawa and Y.Nitta, Chem.Pharm.Bull. 33 (1985) 5042; CA 105 (1986) 190876.
601
S.Yoshifuji, K.Tanaka, T.Kawai and Y.Nitta, Chem.Pharm. Bull. 33 (1985) 5515; CA 105 (1986) 97895.
602
N.Tangari, M.Giovine, F.Morlacchi and C.Vetuschi, Gazz. Chim.Ital. 115 (1985) 325; CA 104 (1986) 50776.
603
N.G.Gerleman, L.V.Krasnyi-Admoni, Yu.B.Yakovlev and G.A. Shagisultanova, Kinet.Katal. 26 (1985) 1085; CA 104 (1986) 167821.
548 604
K.Hegetschweiler
605
M.Ignaczak 4 (1985)
and S.Komisarski, 47; CA 104 (1986)
606
W.Aadam
607
R.Gamboniand
608
and P.Saltman,
and B.B.Lohray,
K.Nytko
C.Tamm,
609
F.Freeman
and L.Y.Chang,
610
F.Grases,
J.Palou
(1986) 611
612
107.
Chim.
98 (1986)
Lett.
185.
27 (1986)
3999.
Zesz.Nauk.Polytech.Bialostockiej: 113;CA
105 (1986)
J.Am.Chem.Soc.
and E.Amat,
34890.
108
Transition
(1986)
4504.
Met.Chem.
11
253.
D.Laloo (1986)
Acta Univ.Lodz.,Folia
Tetrahedron
9 (1985)
25 (1986)
148073.
Angew.Chem.
and H.Sobolewska,
Mat.Fiz.,Chem.
Inorg.Chem.
and M.K.Mahanti,
Afinidad
42 (1985)
593; CA 105
23796.
R.L.Bartzatt
and J.Carr,
Transition
Met.Chem.
11 (1986)
116. 613
614
J.Riefkohl,
L.Rodriguez,
J.Org.Chem.
51 (1986)
T.Ya.Volkova, Mokslu
615
G.I.Rozovskii
Akad.Darb.,Ser.B
H.K.Baek, (1986)
K.D.Karlin
G.Sampoli
and F.A.Souto,
and A.A.Sakharov,
(1985)
(2) 3; CA 104
and R.A.Holwerda,
Liet.TSR (1986)
Inorg.Chem.
206679. 25
2347.
616
I.Kawafune,
617
S.Miyano,
Chem.Lett. H.Fukushima,
Chem.Soc.Jpn. 618
L.Romero,
2468.
H.K.Lee, CA 105
B.H.Chang
T.Matsue,
620
J.T.Groves
621
S.Torii,
1503.
H.Inagawa
and H.Hashimoto,
Bull.
59 (1986) 3285.
(1986)
619
(1986)
and H.R.Kim,
Pollimo
9 (1985)
97102;
97102.
T.Kato,
U.Akiba
and J.A.Gilbert, T.Inokuchi
and T.Osa,
Chem.Lett.
Inorg.Chem.
and T.Sogiura,
(1986)
25 (1986)
J.Org.Chem.
123.
51 (1986)
155. 622
W.Kutner, R.W.Murray, 205
(1986)
J.A.Gilbert,
A.Tomaszewski,
T.J.Meyer
J.Electroanal.Chem.Interfacial 185; CA 105
(1986)
122768.
843.
and
Electrochem.
549
623
R.A.Reed
and R.W.Murray, 200
Electrochem. 624
K.Araki
J.Electroanal.Chem.Interfacial
(1986) 401; CA 105
and S.Shiraishi,
(1986)
14059.
Bull.Chem.Soc.Jpn.
59 (1986)
229. 625
M.E.Fakley,
Organomet.Chem.
14 (1986)
373; CA 105
(1986)
96671. 626
B.V.Romanovskii,
Acta
Phys.Chem.
31 (1985)
215; CA 104
(1986) 11038. 627
K.H.Schmidt,
Chem.Ind.(Diisseldorf)
37 (1985) 762: CA 104
(1986) 111735. 628
Crit.Rep.Appl.Chem.
R.Whyman,
12 (1985)
128; CA 104
(1986)
136669. 629
J.J.Zidlkowski, CA 104
630
(1986)
G.W.Parshall CA 104
631
Prof.Conf.Coord.Chem.lOth
and R.E.Putscher,
(1986)
R.L.Pruett,
(1985)
519;
175210. J.Chem.Educ.
63 (1986)
189;
185542.
J.Chem.Educ.
63 (1986)
196; CA 104
(1986)
188594. 632
I.Ojima
and K.Hirai,
104 (1986) 633 634
I.Ojima,
J.Mol.Catal.
37 (1986)
5 (1985)
102; CA
25,
A.A.Kelkar,
R.M.Deshpande,
[Proc.Natl.Symp.Catal.\,
S.B.Dake
and R.V.Chaudhari, 7th
(1985)
43; CA 105
60267.
B.Juran (1986)
636
Synth.
Adv.Catal., (1986) 635
Asymmetric
147885.
and R.V.Porcelli, (10, Sect.1)
B.D.Dombek,
Hydrocarbon
85; CA 104
Process.,
Int.Ed.
(1986) 70655.
J.Chem.Educ.
63 (1986)
210; CA 104 (1986)
Wiad.Chem.
39 (1985)
667; CA 105
188596. 637
A.F.Borowski,
(1986)
210722. 638
H.Des
Abbayes,
Isr.J.Chem.
26 (1985)
249; CA 104
(1986)
231265. J.Organomet.Chem.
639
H.Alper,
640
Yu.N.Kukushkin, 140857.
Hoord.Khim.
300
(1986)
12 (1986)
1. 147; CA 104
(1986)
64
550 641
S.Inoue
and H.Koinuma,
CA 105 642
(1986)
D.Mahajan
B.James,
Transition", 643
1st
R.Kh.Freidlina, Chukovskaya,
Rev.Inorg.Chem.
6 (1984)
291;
30703. and C.G.Young, (1985)
R.G.Gasanov,
Usp.Khim.
Simp.Quim.Inorg.“Met.
32; CA 104
24789.
(1986)
N.A.Kuz'mina
54 (1985)
and E.Ts.
1127; CA 104
(1986)
148933. 644
M.Huang,
C.Ren,
Y.Jiang,
Organosilicon
Y.Zhou,
Symp.Organosilicon (1986) 645
646
X.Cao,
D.Dong,
Bioorganosilicon
L.Zhao,
Chem.,
Chem.]
7th 1984,
(1985)
Y.Liu
and
!Proc.Int.
275; CA 104
148942.
Yu.I.Yermakov
and L.N.Arzamaskova,
27 (1986)
459; CA 105 (1986)
J.Halpern,
Chem.Ind.(Dekker)
Stud.Surf.Sci.Catal.
232995. 22 (1985)
3; CA 104 (1986)
50455. 647
J.Halpern,
Asymmetric
Synth.5
(1985)
41; CA 104 (1986)
185627. 648
K.E.Koenig,
Asymmetric
Synth.
5 (1985)
71; CA 104 (1986)
185628. 649
H.Brunner,
J.Organomet.Chem.
300 (1986)
650
H.B.Kagan,
Asymmetric
5 (1985)
Synth.
39.
1; CA 104
(1986)
222; CA 104
(1986)
167664. 651
W.S.Knowles,
J.Chem.Educ.
63 (1986)
207621. 652
P.Caubere,
Pure.Appl.Chem.
57 (1985)
1875;
CA 105
(1986)
97057. 653
S.K.Srinivasan, Adv.Catal., CA 104
654
(1986) 655 656
(1986)
M.Troupel,
S.Narasimhan
and N.Venkatasubramanian,
[Proc.-Natl.Symp.Catal.1,
7th
(1985)
315;
186057.
Ann.Chim.(Rome)
76 (1986)
(5-6) 151; CA 105
160667.
E.Steckhan,
Angew.Chem.
D.Schnurpfeil, Leuna-Merseburg
98 (1986)
681.
Wiss.Z.Tech.Hochsch."Carl 27 (1985)
282; CA 105
Schorlemmer" (1986)
78449.
551
657
I.P.Skibida,
Usp.Khim.
658
T.Mlodnicka,
J.Mol.Catal.
659
B.Meunier,
54 (1985)
1487;
36 (1986)
Bull.Soc.Chim.Fr.(l986)
CA 104
(1986)
50405.
205, 578; CA 105 (1986)
171443. 660
V.N.Sapunov,
N.N.Lebedev,
Int.Congr.Catal.8th 661
K.B.Sharpless,
I.Yu.Litvintsev
5 (1984) V359;
and V.D.Vardanyan,
CA 105
(1986)
Chem.Br.
22 (1986)
38,43;
CHEMTECH
15 (1985)
692; CA 104
CA 104
103314. (1986)
185643. 662
K.B.Sharpless,
663
M.G.Finn
and K.B.Sharpless,
247; CA 104
(1986)
A.Pfenninger,
Synthesis
665
B.E.Rossiter,
Asymmetric
666
Synth.
6198.
5 (1985)
185629.
664
(1986)
Asymmetric
(1986)
(1986)
89; CA 104
Synth.
5 (1985)
(1986)
167667.
193; CA 104
167693.
H.B.Kagan,
E.Dunach,
S.H.Zhao,
C.Nemecek,
Pure Appl.Chem.
P.Pitchen,
57 (1985)
O.Samuel
and
1911; CA 105 (1986)
97058. 667
J.Tsuji,
668
S.M.Hecht,
669
R.H.Holm
670
P.Capdevielle 105
671
Acc.Chem.Res. and J.M.Berg,
(1986)
D.Mansuy CA 105
672
J.Organomet.Chem.
185907.
(1986)
19 (1986)
383.
Acc.Chem.Res.
and M.Maumy,
281.
19 (1986)
Actual.Chim.
363.
(1986)(4)
5; CA
171439.
and P.Battoni, (1986)
J.T.Groves,
3000
Bull.Soc.Chim.Belg.
95 (1986)
959;
225445.
Ann.N.Y.Acad.Sci.
471
(1986)
99; CA 105
(1986)
TRANSITION
METALS
IN ORGANIC
SYNTHESIS:
HYDROFORMYLATION,
REDUCTION
AND OXIDATION ANNUAL
SURVEY
LkSZLb
MARK6
Institute H-8200
COVERING
of Organic
Veszprem,
THE YEAR
1986x
Chemistry,
University
of Veszprem,
Hungary
CONTENTS
I.
Theoretical
II.
Hydroformylation
1.
Calculations
Hydrogenation
3.
Reactions
of CO to Hydrocarbons
Nitrogen-containing 2.
401
and Related
Organic
of CO
402
and to Oxygen-
or
Compounds
402 404
Hydroformylation a)
Co Catalysts
404
b)
Rh Catalysts
405
c)
Other
d)
Heterogeneous
Metals
e)
Modified
Systems
Coordination
5.
Water
408
Complexes)
410
(Homologation)
Carboxylic
4.
(Supported
Hydroformylations
Hydrocarbonylation Aldehydes,
401
as Catalysts
Acids
Chemistry
of Alcohols,
and Esters
Related
with
Ethers, 411
CO + H2
to CO Hydrogenation
and
Hydroformylation Gas
Shift
6.
Reduction
7.
Miscellaneous
with
III. Hydrogenation 1.
H Exchange,
2.
Hydrogenation
*
416
CO or CO + H20 Reductive
Tranformations
417 of CO and CO2
and Reduction D and T Labeling
419 420 420 421
of Olefins
Fe, Ru, and OS Catalysts
421
b)
Co, Rh, and Ir Catalysts
422
c)
Ni, Pd, and Pt Catalysts
424
a)
3.
414 Reaction
Asymmetric
Hydrogenation
of Olefins
No reprints available Previous reviewseeJournalof (Elsevier, 1987) 271.
References p. 5 I4
OrganomstallicChenistqLibrary 19
425
433
4.
Hydrogenation
of Dienes
and Alkynes
5.
Hydrogenation
of Arenes
and Heterocyclic
6.
Hydrogenation
of Carbonyl
-7
/.
Hydrogenation
of Nitro
8.
Miscellaneous
Hydrogenations
9.
Dehydrogenation
10.
11.
Hydrogen
338 438
443
Reactions
Hydrogenation
of C=C or C=C
b)
Hydrogenation
of C=O bonds
c)
Hydrogenolysis without
by Hydrogen Molecular
a)
Transition
Metal
b)
Low Valent
Transition
c)
Inorganic Metal
434
Compounds
a)
442
bonds
443 Transfer
444
Hydrogen
444
Hydrides Metal
Reductants
444 Complexes
in the Presence
444 of Transition
Complexes
d)
Reduction
e)
Organic
446
via Silylation Reductants
449
in the Presence
of Transition
Metals f)
Oxidation
1.
Catalytic Groups
2.
451
Electroreduction
IV.
Oxidation
of Hydrocarbons
or Hydrocarbon
02
454
a)
Oxidation
of Alkanes
b)
Oxidation
of Olefins
c)
Epoxidation
d)
Oxidation
with
353
and Photoreduction
454
with
Catalytic
454 454
or Alkynes
457
of Olefins
458
of Aromatics
Oxidation
of O-containing
Functional
Groups
02
461
a)
Oxidation
of Alcohols
b)
Oxidation
of Phenols
c)
Oxidation
of Aldehydes
d)
Miscellaneous
461 463 and Ketones
466
Oxidations
466
3.
Catalytic
Oxidation
of N-containing
4.
Catalytic
Oxidation
of P- or S-containing
Compounds
433
440
Transfer
Reduction
Compounds
Compounds
Organic
Compounds
461
Organic 471
401 5.
Catalytic
Oxidation
or Inorganic
6.
of Organic
Compounds
Organic 472
a)
General
b)
Oxidation
c)
Epoxidation
d)
Oxidation
of O-containing
Functional
e)
Oxidation
of N-containing
Organic
f)
Oxidation
of P- or S-containing
472 of Hydrocarbons
Oxidation
Transition
Oxidation
or Hydrocarbon
Groups
472
of Olefins
Stoichiometric High Valent a)
with
Oxidants
415
Organic
of Organic
Metal
of Hydrocarbons
Groups
485
Compounds
488
Compounds
Compounds
489
with
Complexes
491
or Hydrocarbon
b)
Epoxidation
c)
Oxidation
of O-containing
Functional
d)
Oxidation
of N-containing
Organic
e)
Oxidation
of P-, S- or Halogen-containing
Groups
491
of Olefins
496 Groups
498
Compounds
503 Organic 505
Compounds 7.
Electrooxidation
V.
Reviews
List Metal
507
and Photooxidation
508 511
of Abbreviations
512
Index
514
References
I. Theoretical
Calculations
Theoretical
calculations
showed
that the
1,2-hydride
shift
reaction: -
HMn(COjS
is considerably
more
(C0)4Mn-C(O)H
endothermic
than the
1,2-methyl
shift reac-
tion: CH3Mn(C0)5
This
explains
the apparent
CO [ll. Quantum tive addition
chemical
of pentane
[2]. An extended reactions systems
Refcrcnces p.
considered
(Co),Mn-C(O)CH,
inability
calculations onto
species, a mechanism
of hydride
to migrate
were performed
HPt(PPh3)X
Hiickel MO analysis
by do MLn
5 I4
-
toward
on the oxida-
(X = Cl,Br,I)
complexes
of H-H and C-H activation
such as Cp2LuR involving
was reported.
a transition
For the
state with
402
an electron-deficient
coordination
[31. A semiempirical to ethene
study
was performed,
VB analysis
-
which
dials
has been
[51.
II.
Hydroformylation Hydrogenation
cates.
The Co(I)
trifluoroacetate
nium(III) styrene
significant ions were through
these Ru(II1) observed backbone. various
Carbon
were
amounts
in 0~0~ to vicinal
orbital
point
of
of CO
was
either
incorporated
or Nitro-
CpCo(COD) were
formed
rings
sili-
161. Ruthe-
linear
poly-
and the reactions studied.
and hydrogen
Co(I)
in situ from -was used. At low
into sulfonated process
with
on alumina
prepared
CO and H2 were
hydrocarbons
studied
or supported
0 2 and the benzene
aliphatic
liqands
and to Oxygen-
of olefins
an ion-exchange
monoxide
by
Compounds
or the complex
ions with
between
Reactions
in solution
catalysts
augmented
of olefins
from the frontier
of CO to hydrocarbons
at 200-250°C
from 0x0 porphyrins
/4!. The concerted
in the oxidation
Organic
Co(I1)
pressures
functions
of CO to Hydrocarbons
Hydrogenation
found to be reasonable
to the oxygen
and Related
gen-containing
catalysts
wave
analyzed
view
1.
step
was
transfer
on EHT calculations
of an olefin
is the Eirst
-
based
of the resultant
[3+21 cycloaddition
mode
of oxygen
of
H/D Exchange
was
of the polystyrene
reacted
to give
at 150'
and oxygen-containing
compounds
171. Benzene
solutions
CO catalytically
produce
with
300 nm light.
tion
between
rium)
The
[Rh(OEP)12
and HCORh(DEP)
of ethylene
gas in the presence
qlycol
of Ru carbonyl
by ammonium,
phosphonium,
activity
for ethylene
glycol
cant effect; the best anol) also
solvents
results
ability with
[9]. The
in N-methylpyrrolidone by the addition
catalysts
formation
as solvent
of a large
excess
bond
[8l.
500 bar)
halides.
was observed
was markedly
(Ph3P)2NC1.
a siqnifi-
12 and 15 gave
glycol
of imidazole
is
Highest
with
had also
between
of ethylene
equilib-
from synthesis
(240°C,
and iminium
numbers
irradiated
by the reac-
of the Rh,C
of the solvent
acceptor
when
in a thermal
and ethanol
formation
of H2 and
occurs
(formed
cleavage
promoted
The electron-accepting
and methanol
of CH20 probably
by the homolytic
formation
in the presence
formaldehyde
Formation
HRh(DEP)
initiated
of
(and meth-
increased compounds,
403 especially
benzimidazole
an ammonium anionic
Ru species
genated
products
systems
in AcOH
the activity stability
[lo]. Probably
ion and acts
as the cation
[ll]. Conversion
was
studied
as solvent.
of pressure
Different oxygenates
proposals
increasing
The reaction
(220-240°C,
mixture glycol
[18]. Rhodium excess
in addition
ethylene with
glycol
catalyzed
References
p. 5 I4
ligands.
by
2000 h-l with
70% selectiv-
[16]. In the hydrogenation complexes
[17,18]
were
while
formation and hence
and the sta-
dependent
Best results
led to the
significant
were
catalytic
on the
obtained
arylphosphines
of the phosphidoinhibited
as solvents
from synthesis
cataly-
of tertiary
by Ir carbonyl
]lP]. By monitoring
gas at 200°C of [Rh(CO)4]-
ammonium
however,
cation
in the hydrogena-
1,2-Dimethyl-2-imidazolidti
it was observed
anion was,
donor
activity
(at 80°C).
used
concentration
as a proton
The effect
accelerated
complexes
if a tertiary
bly acted
of ethylene
+ N-methyl-2-pyrroli-
of the reaction
[Rh9P(CO)21]2-
The tetracarbonylrhodate active
Rh were pres-
by Rh-phosphine
like PPri
and conductivities
increasing
of C2
found to be strongly
to alcohols
or tetraglyme
red spectra
of the formation
formed -in situ from Rh(C0)2(acac) and of tri-n-alkylphosphines (lo-40 moles/mole Rh)
tion of aldehydes none
were
anion
pres[13].
The synthesis
was about
catalyzed
of phosphites
cluster
cases
H2 partial pressure
a Rh4(C0)12
was colorless
alkylphosphines
and all types
In both
with
Co
At 300°C and 2000 bar the turnover
of the phosphine
carbonyl
studied.
of CO partial
500 bar) the selectivity
bulky
a large
to
its
of CO + H2 with
be significantly
glycol
of the catalyst
structure
showed
could
for ethylene
was
[14,15].
gas using
as catalyst
of CO to ethylene
sis
catalyst
contributed
enhanced
gas over oxide-supported
the temperature.
frequency
with
metal
mainly
increased
for the mechanism
papers
from synthesis
system
glycol glycol
independent
from synthesis
in two polemic
bility
1O:l Ru:Rh mixed
on the conversion
to ethylene
sure but was practically
ity.
to
active
gas into C2 oxy-
and the Ru component
to ethylene
the selectivity
done
is converted
1121.
and Rh catalysts
glycol
of synthesis
The Rh component
of the catalyst
The effect
ented
with
the amine
of the catalytically
that
infra-
the yield
and 200 bar
increased
in the reaction catalytically
was also present:
of
mixture. only
this proba-
[20]. phosphines
catalysts
on the hydrogenation
(250-270°C,
650-750
of CO
bar) has
404 been
Triarylphosphines
investigated.
activity
and
selectivity
trialkylphosphines
found
to have
The clusters were
used
composed
LPtRh5(C0)15]-,
The results cluster
with
those
and Pt(acac)2.
product
and was
glycol
i211. 2-
IPtRh4(CO)121
at 230°C and obtained
with
Ethylene
but Pt increased
that Pt acts
whereas The complex
mixture
and
the
1400-2000 catalysts
glycol
MeOH
was
in
formation.
in the form of a mixed
Pt-Rh
[221.
Both catalyst
Ru02.xH20
and RUDER
precursors
formaldehyde
and Me3N
is the primary
reaction
participates
ly leads
to ammonium
carbonyls
See also
have
for the conversion
to N-methylformamides
osmium
formation,
for ethylene
[Rh5(C0)15]-,
compared
favored
suggest
activity
enhanced
formation.
for CO hydrogenation
were
of Rh(acac)(C0)2 the
glycol
methanol
from the reaction
catalytic
as catalysts
cases
promoted
isolated
a high
bar. The results
most
for ethylene
mostly was
IrZ(C016(PPh3)2
such as PPh3
showed
to be effective
340 bar.
product.
in a water-gas
also
found
of CO + H2 + NH3 mixtures
at 230°C and
reaction
carbamate
been
shift
Probably formed
reaction
as byproduct. some catalytic
Water
in the
and subsequent-
Rhodium, activity
iridium
and
[23,24].
12011.
2. Hydroformylation a) Co Catalysts
Capillary
GC and GC-MS
ed by hydroformylation alcohols
that
formylation decreased amines
could
be formed
of propene by py,
increased
on the rate was
found
were
present
and BuNH2;
The
of HCo(CO)d formation
than
acid was
showed
suitable
Co dodecanoate simpler
mixture
that
obtain-
all 24
[251. The rate of hydroas catalyst
the inhibiting
order.
to be a more
of propene
of the alcohol
n-alkenes
Co 2-ethylhexanoate
in the stated
hexanoate formylation
using
(iBu)3N
was noted
of 2-ethylhexanoic
analysis
of Clo_13
effect
same effect
because
of these
of the amines
[261. Cobalt catalyst
was
2-ethyl-
for the hydrothe regeneration
than that of dodecanoic
acid
[27]. Hydroxycitronellol -l-heptene catalyst
was prepared
by hydroformylation
from 2,6-dimethyl-6-hydroxy-
in the presence
of a Co/phosphine
[28j. The use of Bu2P(CH2)2SiMe(OMe)(CH2)2PBu2
as ligand
405 in the hydroformylation resulted
of propene
in 97% selectivity
for straight-chain
The aminophosphine-containing
Co carbonyl and
[Co(CO)3(Ph2PCH2CH2Ne3)21(PFs)2 were The
tested ionic
as catalysts
complex
two-phase
system
but
[301. The chiral prepared
could
optical
See also
b)
was
[291.
of l-hexene.
in an aqueous-organic catalysts
solvent
was rather
(1, L = (RI-(+)-PMePh(o-anisyl))has
as catalyst
for the hydroformylation
L was observed
induction
products
[Co(CO)3(Ph2PCH2CH2NMe2)12
of both
at 89'C and 80 bar CO + H2. Under of the ligand
catalyst
complexes
for the hydroformylation be used also
the activity
cluster
and used
with Co carbonyl
such conditions
and cluster
reported
been
of styrene
decoordination
(2) was obtained.
No
CO and H2 in the presence
of
[31].
[43,451.
Rh Catalysts The reaction
Rh4(CO)12
cyclopentenones tuted
of enynes
as catalyst
with
at 100°C and 200 bar gave
and unsaturated
lactones
[321
formyl
dienes,
(R=Ph or p-substi-
Ph):
R _,IR-
-R
+
Ra
References p. 5 14
I R 0
RYR
+
low
gR ‘
Chemical propene ment
oscillation
with
a Rh-phosphine
for oscillation
of butyraldehyde formylation
Using
formylation followed
by hydrogenation
of 1-hexene
31P NMR.
with
The CO-free
yield
complex
to the monocarbonyl
tion mixture
[361. Hydroformylation
l-11 bar and 40°C with high n/i
caused
ratios
a systematic
reaction
mixture
drop
of this ratio.
[Rh2( lJ-L)2(COD)212'
and
Addition catalytic 5 bar.
of tBuSH
activity
complex
allylbenzenes
by independent
were
[Rh( /.t-SBut)(CO)Lj2
High
yields
pressure using
of linear
catalytic
(L = PPh3, aldehydes
including
using
of the
was the active Rh complexes
(L = 3) were
1381.
increased
of 1-hexene
its
at 80°C and
of the dinuclear probably
[39]. Several
substituted
the dinuclear
Rh complex-
P(OPh13)
obtained
at 80°C
of 1-hexene
and stoichiometric
Cp2Zr(CH2PPh2)2.
prepared
of l-hexene
slightly
P(OMe)3,
were
hydroformylation
[Rh(b -SBU~)(CO)~]~
diphosphines
pathways
at
increase
The two Rh complexes
hydroformylated
could
as catalyst.
IR examination
the formation
[Rh( K-SBut)(CO)(PPh3)12.
act as catalysts
es
for hydroformylation showed
which
CO to the reac-
ring binuclear
to HRh(CO)(PPh3)3
using
was examined
for the hydroformylation
IR and NMR spectra
studied
-+ P(OPh)3
!Rh2(I_I-L)2(CO)4]2c
gave
hydroformyla-
formed
that HRh(CO)!P(OPh)3]3
1371. The large
as catalysts
cleavage
at 1 bar: pressure
form of the catalyst
and used
was
of l-hexene
obtained
suggested
has been
of
catalyst
and ether
by admitting
Rh(acac)[P(OPh)312
were
catalyst
!341. Hydro-
a Rh carbonyl-PPh3
HRhlP(OPh)3]4
back
amount
the formation
be diminished
HRh(CO)[ (P(OPh)3]3
require-
133!. Hydro-
of
[35]. Stoichiometric
be converted
Very
as promoters
of
is accompanied
deterioration
could
with
mixture
catalysts
of the aldehydes
in 75% overall
important
of a certain
reaction
Rh-PPh3
phosphines
compounds
of CH2=CHCH20But
HO(CHZ)40H tion
with
and a rapid
bidentate
and phosphonium
The most
was the presence
in the liquid
alcohol
side reactions
activity. Ph3PO
trimer
in the hydroformylation
catalyst.
to occur
of ally1
by several
was observed
as catalysts. i401. LOW
was performed
amounts
The latter
of various
ligand
furnished
407 the most
active
catalyst
Nitrogen-containing
system
[41].
cyclic
olefins
(N-substituted
nes and N-methyl-1,2,3,6_tetrahydropyridine)
were
nortropidi-
hydroformylated
with
Rh + PR catalysts prepared in situ. Regio- and chemoselectiv3 ity of the reaction was practically independent of the phosphine in the case of nortropidines;
dine
the selectivities
by the presence See also
c)
Metals
catalyst
production
ligand
and
[421.
UV irradiation
at ambient
catalytic
solvents
for these
Co2(CO)9
temperature
the bimealcohol
ranged
between
effect against
The platinum
might
catalysts.
be explained
complex
and heptane
system
(4, Y=H) was
were
(4,Y = EtCO)
formed
an in-
of olefins, were
the best
It was proposed
that the
reactivity
of
[45].
to give products Along
with
in comparable
the alkyl could
conditions
showed
found to catalyze
and heptene-2
as substrate,
under
Hydrogenation
these
Alcohols
by the high
acyl complexes
(90 and 60%, respectively).
was used
under
alone.
by the
and RUDER
for the hydroformylation
cobalt
of heptene-1
is catalyzed
and pressure.
bimetallic
or RUDER
mixed-metal
[HRu(CO)~I-
and propene Ru(C0)4(PPh3)
+ Ru~(CO)~~
synergistic
(4,Y = Et) and
with
Linear
ratio
was also observed
activity
with
C8 alcohols
of ethene
and olefins
compared
linearity
if the Cr/Co
Ru(CO)~(PP~~)~,
[44]. The Co2(CO)S
formylation
investigated
[43].
complexes
of aldehydes
was
+ HCO(CO)~(PBU~).
efficient
Hydroformylation
ethene
by the phosphine
such as Et3N
of 1-hexene
Cr(C0)5(PBu3)
was most
5O:l and 1OO:l
creased
influenced
bases
tetrahydropyri-
as Catalysts
Hydroformylation
Ru(0)
the less basic
[106].
Other
tallic
were
of added
with
the hydroof high
CS aldehydes amounts.
also
If
and acyl complexes
be isolated.
Catalysts
formed
in situ from Pt(COD)2, Ph2POH and a tertiary phosphine were also -active and in the absence of a tertiary phosphine ethene produced mainly
3-pentanone
Referencesp.514
under
hydroformylation
conditions
1461.
Ph2 p\ pt,PPh3
.o H; O-P’
Y ‘ Ph2
See also
d)
11871.
Heterogeneous
Systems
The supported used
as catalyst
and 20-60 during
bar.
(Supported
tetranuclear
Complexes)
Co-P cluster
for the hydroformylation
The activity
repeated
of olefins
of the catalyst
use (up to 10 times)
(5) was prepared
and
at llO-15O'C
did not decrease
[47].
(CO)2 ,Qo,2 SIL
/ u-
’
P
-
-‘ cco,2co~c
/
5 co (CO)2
0
Phosphine-bearing carriers
for cobalt
transformed which
under
behaved
Formation products
polyphosphazenes
hydroformylation
the reaction
conditions
like the homogeneous
of HPR2,
benzene,
was observed
(6) and
catalysts.
benzyl
into
analogues alcohol
(7) were Both
soluble
COAX and other
used
systems
complexes + XPR2.
deqradation
[48].
PhO
PhO
/ \ ,0 -cl- P N# N ‘ fl ,OPh 1
PhO,
PhO, PPh2 6
PhO/PNN/P\OPh 7
as were
PPh2
409
Hydroformylation catalyst
systems
clusters
bonded
tertiary
amine
obtained
The industrial
lary
PPh3
and
forces,
lysts based Polymeric
tested
containing ring was
aldehyde
formation
has
stable
available
group
the unsaturated
showed
good
selectivities
The activity tion was found dependence
solvents.
of Rh-zeolite
to depend
upon
the partial
to that
reported
Rhodium
zeolite
A catalysts
by ion exchange
liquid
phase.
similar
but
more
rapidly
containing
in the liquid [56 1.
by a RhNaY
proceeded
zeolite
to heterogenize
References
p. 5 I4
Pt catalysts
were
catalyst
onto poly-
[547.
for hydroformyla-
surface
The rate were [551.
Rh prepared
as catalyst
phase
catalyst
were
reaction
for
and in the
IR studies
polymeric
pre-
in THF
formation
applied
transform
of
cata-
of the two catalysts
in a homogeneous-like
for
E-styryl-
phosphine
the ion-exchanged
Polystyrene-divinylbenzene-based used
either
activity
phase
with
of preparation.
in the vapor
In situ Fourier
resins
hydroformylation
Rh were
of hexene-1
for
of CO, H2 and propene
for homogeneous
The vapor-phase
hydroformylation reaction
pressures
for
studied
prepared
X and Y catalysts
or intrazeolitic
the hydroformylation
aldehyde
on their method
similar
was
The supports
The supports
for normal
on the
hydroformylation
pared
grafting
used
[51]. The
and selective
Rh(C0)2(acac)
copolimers.
in different
(Et2N)2PC1.
and the hydrogenation
of Rh(1)
by reacting
an amino
were
functionalized
diphenylphosphine-polyropylene by y -radiation
with
ligands
lifetime
amine
Cata-
as substituent
active
in
capil-
of propene.
of diisobutylene
of dicyclopentadiene 1531. A series
dissolved
by strong
copolymer
to be the most
been prepared
propylene
hydrogenation
by reacting
and these
[52]. The catalyst
formed
life
for 1500 h 1501.
prepared
the -CH2NHCH2CH20H
commercially
the aldehyde
support
were
were
[Rh(C0)2C1]2
found
the hydroformylation
lysts
supports
for the hydroformylation
catalyst
Rh-loaded,
of HRh(CO)(PPh3)3
on a porous
ligands
from
aromatic
available
of catalyst
step but later aldehyde
divinylbenzene-styrene
prepared
as catalysts
or commercially
for the hydroformylation
on CL -alumina
group-containing
using
(n = 0,1,2,4)
first hours
applicability
immobilized
was
studied
[491.
aminophosphine
Complexes
the
was the slow
rate determining
liquid
amines
During
resins.
was
from RhnCo4_n(CO)12
to tertiary
hydroformylation became
of dicyclopentadiene
lost Rh
of propene
reported. pathway
phosphines
for hydroformylation
was
of
The [57]. were U -olefins
410
in the presence
of SnC12.
The catalysts
(95%) to linear
aldehydes
[58]. Copolymerization
(8)
with
which
styrene
was
catalyzed
with
PtC12
JO-75%
was of
selectivity
of the phosphine
The resulting
and SnC12.
the hydroformylation
aldehyde
high
gave a phosphinated
and divinylbenzene
loaded
displayed
of styrene.
enantiomeric
purity
polymer
chiral
The resulting
complex
hydrotrop-
[ 59 ij .
8 PPh2 The chiral styrene
ligand
was used
catalyst
(9) attached
for asymmetric
to linear
or cross-linked
hydroformylation
O-JO%
in the case
Optical
yields
vinyl
acetate
or N-vinylphthalimide
as olefins.
several
loss of enantio-
catalysts
could
selectivity
be reused
but their
catalystic
times
between
poly-
Pt + SnC12
systems.
of styrene,
ranged
with
without
activity
gradually
The
decreased
!601.
--_ n Q-&j-J 9
H
-
P
/
p \
\/
-
e)
Modified
Ph2PR,
hydroformylation Selectivity See also
-
Hydroformylations
Polynuclear (Ph2PH,
\/
Co carbonyl Ph3P,
Bu3P,
and consecutive
of pentadecanol
[105].
complexes
dppe)
were
containing used
hydrogenation
formation
was
phosphine
as catalysts
ligands
for the
of I-tetradecene.
31-348
1611.
411
3. Hydrocarbonylation
(Homologation) of Alcohols, Ethers, Alde-
hydes, Carboxylic Acids and Esters with CO + H2 The catalytic activity of [Ru(CO)313]- in homologation of MeOH, Me20, MeOAc, formates, and alkyl orthoformates was discussed [62]. The selectivity of acetaldehyde formation in the hydrocarbonylation of methanol with Co12 as catalyst (150°C, 200 bar CO + H2) could be improved by adding diphosphines Ph2P(CH2),PPh2 (n = l-6) to the catalyst system. The main species present under the reaction conditions was [Co(CO)xPyliCo(CO)4] (x + y = 5; P = a phosphine moiety) [63]. The influence of several furfurylphosphines and their phosphonium salts, and of furylphosphines on the homologation of methanol to ethanol was investigated using Co as catalyst metal and I2 as promotor. The best results with respect to selectivity and conversion were obtained with the bidentate ligands (10) and (11) [641.
Ph2P g
Homologation of MeOH to EtOH using the Co12 + Ru12(C0)2(PPh3)2 + NaI catalyst system was found to be second order in MeOH. The complex [MePh3P][Ru13(CO) 3 ] was isolated from the reaction mixture and proved to be an active homologation catalyst also in the absence of cobalt [65]. The influence of (12) and (13) on the homologation of MeOH to EtOH was investigated using Co(OAc)2.4H20 + RuC13. 3H20 (2O:l) as catalyst and I2 as promoter. The potentially bidentate phosphine (12) gave a much more active catalyst system than the potentially tridentate phosphine (13) [661.
12
13
The ligand (14) was tested in the homologation of MeOH with Co + Ru catalyst and MeI promotor. Under optimum conditions selec-
References
p. 5 14
412
tivity large
of EtOH amounts
formation of Et20
about
was
were
60% but at high
formed
conversions
1671.
14 CH2PPh2
Bifunctional noble
catalysts
i68]. Homologation
MeOH
100 bar) Neither
was
achieved
synergistic
effect
Co2(COj8
adding
low reaction
with
a small
temperature
Hydrocarbonylation
um complexes aldehyde were
crotonization
(12OO)
L711.
these
products
diethyl
qlycol
Co + Rh mixed-metal
tigated
was
at llO°C
obtained found
later
of co2+ which
in a relatively
substituted of qlycol
aldehyde
Rh(CO)(PPh3)2C1 and the reaction -chain
bromide
took place.
state
as
at a rather
at 170-180°C
with
studied. COAX
Heavy
and
Rhodiacet-
byproducts and of
to ethylene
systems
has been
C2 selectivities
first
maintains
a
i72]. Hydroformylation
inves-
(= 65%)
catalysts.Glycolaldehyde few hours
of the reaction:
to methanol This
effect
the rhodium
and of glycolmay
be due to
catalyst
for some
[73]. The use of pyridine
greatly
in the hydroformylation
was
carbohydrates
Highest
as solvents
as catalyst.
benzyl
and its hydrogenation
in the
oxidized
pyridines
to 2-phenyletha-
of aldolization
catalytic
I
to be
using
product.
of formaldehyde
glycol
found
has been
+ Rh4(C0)12
only
hydrogenation
to ethylene
the presence time
CoC12.6H20
to be formed
only
aldehyde
and 100 bar.
with
1691. In
(84-87%)
propane
mainly
of acetaldehyde
to qlycolaldehyde
were
of 6:l
and working
ether:
was the main consisted
formaldehyde using
system,
of water
mainly
acetal
formed,
catalyst
amount
system.
significant
of Co, Ru and
alcohol
selectivity
Rh and Co complexes
furnished
dimethyl
also
of benzyl
of 2,2-dimethoxy
120 bar CO + H2 using
ratio
in the presence
of
CO + H2 !200°C,
catalyst
the most
at a Ru:Rh
high
mixed-metal
+ RuC13
with
and 450 bar, Co and Ru were
be performed
promoter,
to ethanol
active,
to PrOH
1701. Homoloqation
synergistic no1 could
were
was observed
CO + 2H2 at 200°C
I and a heterogeneous
for the homologation
a Ru + Rh mixed-metal
alone
of EtOH
of Co,
tested
of methanol with
of the metals
the homologation with
composed
(Ru, Rh or Re) were
metal
enhanced
the
of formaldehyde
Parafonnaldehyde
was used
or
formation with
as substrate
run at 70°C and 50 bar CO + H2 [74]. Straightsuch as trioses,
tetroses,
pentoses,
and
413 hexoses were obtained in good yields by reacting formaldehyde with CO + H2 in the presence of Rh(CO)(PPh3)2Cl and Et3N at 120°C and 120 bar. Carbohydrate formation under such conditions was due mainly to an amine-catalyzed condensation of glycol aldehyde formad by the Rh-catalyzed hydroformylation of formaldehyde [75]. The ruthenium-catalyzed homologation of acetic acid to propionic acid with synthesis gas was shown to proceed through the following consecutive reactions: hydrogenation of acetic acid to ethanol (and esterification to ethyl acetate) and carbonylation of the alcohol to propionic acid. Alkyl iodides were also found in the reaction mixtures and probably played a role in the carbonylation process [76]. Reaction of methyl acetate and synthesis gas at 170°C and 330 bar with a catalyst charged as Co12 + LiI + NPh3 (molar ratio 2.5:1.5:1) resulted in the formation of acetaldehyde and acetic acid according to the following stoichiometry: MeCOOMe + H2 + CO. -
MeCHO + MeCOOH
Acetaldehyde was obtained in 98% yield: minor amounts of methane and ethyl acetate were the only byproducts [771. Homologation of methyl acetate with CO + H2 using rhodium chloride/methyl iodide based catalyst systems under mild conditions (150-160°C, 40-60 bar) was reported. The activity of the catalyst was significantly increased by the addition of phosphine oxides. Predominant reaction under such conditions was the formation of propionic acid:
CH3COOCH3 + 2C0 + 2H2
-
CH3CH2COOH + CH3COOH
In combination with Ru mainly the alcohol moiety was transformed into its next homologue [781: 2CH3COOCH3 + 2C0 + 2H2
-
CH3COOC2H5 + 2CH3COOH
The effect of Lewis acids on the homologation of methyl acetate to ethyl acetate with ruthenium carbonyl iodide catalysts was investigated. Al and Sb derivatives favored the carbonylation steps of the reaction resulting in high (72%) selectivities to acetic acid; Ti derivatives favored carbonylation + hydrogenation increasing ethyl acetate selectivity up to 70% [79]. The homologaReferences
p. 5 14
414 tia
of methyl
-promoted pathway
esters
ruthenium
of the reaction
moter
employed:
ethyl
esters
process
with
the alkoxy
moiety
found
to be the most
catalyst
effective
were
catalysts
the alcohol
be transformed
found
tigated gous
and
180°C,
lactone
Rh catalysts
furnished
4. Coordination
for the
in the presence
Related
of
in the case of with
iodide
was
Rh-based
to the usual
Ru-based
with
CO + H2. could
[82].
catalyzed
by Rh and Co complex-
and 200 bar has been Formation
only with Co catalysts
only mono-
of
Homoloqation
of esters
of I2 as promoter.
Chemistry
tested
important
acid part of the ester
homologue
respectively,
was observed
were
[Sl]. Ruthenium-assisted,
of lactones
in the presence
of
iodide
to be superior
its higher
the formation
(especially
of ionic
and the carboxylic
into
pro-
(2H2 + CO).
for the homologation
Hydrocarbonylation es at 230°C
by Ru
of the iodine
was the most
esters
and 420 bar
of iodine-
The predominant
was
Co + Ru catalysts
and a combination
systems
or Co-based
reaction
acyl reduction
was promoted
esters),
in the presence examined.
on the nature
of carboxylic
at 200°C
ethyl
Both
with Me1
carbonylation
gas
has been
LiI the main
whereas
promoters
synthesis
depended
[80]. Homogeneous
reductive iodine
with
catalysts
(14-48%
and dicarboxylic
acids
to CO Hydrogenation
inves-
of the homoloyield), !83].
and
Hydroformylation
Based it was
on model
suggested
of CO occurs
via
to coordinated on the next
studies
that
with
successive
[84]:
cycle
complexes
catalyzed
intermolecular
CO. A catalytic
page
isolable
the homogeneously
based
of Ru and OS hydrogenation
additions on these
of H- and H steps
+
is shown
415
M
-
H2
M’CHb
H* + MH
M’CO CH30 ‘H
H+ + co
A quantitative relationship was found between the effect of bases on the deprotonation of HCo(C0)4 and their inhibiting effect on the hydroformylation reaction [851. The acylcobalt tetracarbonyls nPrCOCo(C0)4 and iPrCOCo(CO)4 react with H2 or HCo(C0)4 to yield nPrCH0 and iPrCH0, respectively. These reactions are part of the catalytic cycle in the industrially important hydroformylation of propene. The kinetic results support the conclusion that under the conditions of catalytic hydroformylation
( >lOO°C
and > 100 bar
CO + H2) the reaction with H2 is mainly responsible for aldehyde formation [86]. The reaction of HCo(C0)4 with ethyl acrylate under CO results under kinetically controlled conditions (c 10°C) in the branched-chain alkyl Co carbonyl complex; under thermodynamical control (> 25OC)the alkyl complex is transformed into the straight-chain acyl Co carbonyl. This effect agrees with the known influence of temperature on the distribution of isomeric aldehydes in the catalytic hydroformylation of ethyl acrylate [871. Triarylphosphines undergo P-C bond scission under hydroformylation conditions (190°C, 140 bar CO + Hz) in the presence of co2(co)8 to give a variety of hydrogenolysis and CO insertion products. Aryl group Er&lhg
is also observed when PR3 and PR;
are subjected to the above conditions.
In
the presence of an olefin
the phosphorous-aryl bond cleavage proceeds at a much slower rate [88]. Formation of clusters was found to be the cause for deactivation of rhodium carbonyl catalysts used in hydroformylation.
References p. 5 14
416 Oxygen
strongly
steps,
the relatively
could
undergo
vation
promoted
The mechanism studied
complexes ed that acid,
SnC12
-halogen
dride a very
The
synergetic
tive than
the
of activity
amines
catalyst
active
highly
long
with
Fe/Ir
the catalytic
systems,
choice
investigated step
catalytic
About
This
mixed ac-
for the
and secondary
react
do not give which
which
after
a
is a very tempera-
solvents;
it
a relatively
[Ru(bpy)2(CO)H]PF6 leads
active
i941. Reaction
at room
or nonpolar
with CO2
furnished
complex
has
to H2 formation)
is probably
reaction
The
more
of Ru3(C0)12
blue
(which
metals
[931.
CO2
reaction
shift
VIII
50% increase
towards
i95]. The complex
at
the i921.
of magnitude
amines
only
hy-
showed
studied.
inert
activity
and its protonation
in the water-gas
of Group
that primary
in polar
elim-
reaction that
has been
gas shift reaction
is insoluble
kinetically.
zeolite
indicated
was pyridine
a dark
for the water
period
Na-Y
but the amines
aliphatic
and was
its highest
activity
It was shown,
bpy yields
the reductive
alone.
systems
in a a tungsten-
in the case of Fe/Ru
carbonyls
catalyst
induction
[90].
i9ll. The cluster
carbonyls
two orders
The best
been prepared
mining
metal
active
with
was rate-determining
reaction
found
active
catalyst
to Pt
by HFe(CO;
involves
studies
metal
about
Tertiary
The catalyst
reaches
was
reaction.
with
conclud-
as a Lewis
for the water-gas-shift
systems.
of Ru3(CO)l2
of the
It was
bonded
on hydrated
gas shift
were
individual
to form carbamates.
moderately
reactions
CO if irradiated
adsorbed
of mixed
water
increase
yield
complexes
as a co-catalyst:
intermediate
activity
which
gas shift
ture.
mechanism
was observed
Amines water
suggested
synergism
carbonyls
by Pt-Sn
cycle.
is catalyzed
under
effect
pronounced
metal
reaction
~20 and the cluster
in the homogeneous most
ways
and spectroscopic
between
reacti-
stoichiometric
and water
[HFe3(CO)11]-
Kinetic
reaction The
gas shift
high catalytic
60-18OOC.
in partial
catalyzed
and as a ligand
of SnCl<,
of H 2 from a dinuclear
anion
resulted
in
still
reaction
of DMF
lamp.
ination
occured
in the beginning
in the cataiytic
act in several
gas shift
Clustering
[89].
involved
may
The water
which
by investigating
as the source
9:l mixture
formed
of hydroformylation
possibly
5. Water
formation.
clusters
declusterification
of the catalyst
has been
cluster
small
catalyzed
the rate-deterby
417 [Ru(bpy),(CO)C11+ [961. The water-gas shift reaction catalyzed by bis(bpy)-carbonyl-Ru(I1) complexes has been investigated. All the species involved in the catalytic cycle (which is shown below) have been isolated or characterized by spectroscopic methods [971.
H30+T
[Ru (bpy)g W~~O:12~H20
[Ru (bpy)K0)2]**
[Ru(bpy)2KO)Hf
OH[Ru (bpy)2KO)KOOHf
For a correction of AS 1985 ref. 66 see [98]. See also [23,105].
6. Reduction with CO or CO + H2g Reduction of ketones to secondary alcohols was achieved with 4 -Ph4C4CO)(C0)3Ru as catalyst
CO +-H20 at 105OC and 30 bar using ( 3
in THF solution. The reaction was accelerated by addition of Na2C03 [991.
The Al symmetry
vCo vibrations of the carbonyl complexes
(L = substituted derivatives of phen), were determined. MOM A correlation was found between these values and the catalytic activity of the systems composed of RUDER
or Rh6(CO)16 and the
corresponding phen derivatives in the hydrogenation of nitrobenzene with CO + H20
[loo]. The reduction of nitrobenzenes to the corre-
sponding anilines was achieved with a series of Ru and OS phosphine complexes using H2, H2 + CO or CO + H20 at 120°C and 70 bar in 2-ethoxy-ethanol as solvent. Addition of KOH increased the turnover numbers. The reaction was best carried out under water gas shift conditions [loll. Reduction of g-nitrostyrenes
(15) to indole
derivatives (16) by CO is catalyzed by Fe(CO)5, Ru3(CO)12, and Rh6(CO)l6 at 220°C and 80 bar in toluene solution. In small amounts also amines (17) are formed by hydrogen abstraction [102].
References p. 5 14
418
Hydrogenation
of
CI,p -unsaturated
CO + H20 and Rh4(C0)12 amine moieties selectively. effective readily
was
catalyst
studied.
than
supported
the homogeneous
one
to aniline
was
less active
compounds
on polymers bonds
catalysts
were
hydrogenated
generally
more
(18) were
in good yields
under mild
as catalyst
with
containing
were
[1031. Azidoarenes
derivatives
CO + H20 and RhC13. 3H20 catalyst PdC12
carbonyl
The C,C double
The resin-supported
transformed
15OOC).
17
16
15
conditions
with
(20 bar,
[104].
co + w
N3
18 Reduction olefins
with
of various
CO + H20 using
ied. The activity depended
on the
structure
amine
containing gas
tives
for the reduction
shift
urated
aldehydes
diamine
systems
droformylation
shift
with
the
showed
gave
of aldehydes. hydrogenated
high yields
and reduction
catalysts
component. catalytic diamines
activity
100 bar)
The role
2-arylacrylonitrile
d,(3-unsat-
from olefins
N-alkylvia hy-
can be trans-
under
in the presence
of the Rh catalyst
formed
for the
aldehydes;
2-arylpropionitriles
water
is to hydroge-
in the base-catalyzed
CH20 N-Me - morpholine
-
Ar-C-CN
gas
of RhC13.3H20
reaction
[1061:
Ar -CH2-CN
di-
the best addi-
With pyridines,
to saturated of alcohols
strongly
The ethylene
were
of
was stud-
systems
[1051. Arylacetonitriles
into
(200°C and
precursor.
+ amine
high
N-alkylated
formaldehyde
conditions
as catalyst nate
catalyst
and carbonylation
of the catalyst
of the amine
reaction;
were
groups
Rh6(C0)16
and selectivity
water
formed
functional
Rh -Ar-CH-CN CO+H20 kH3
419
Nitrobenzene derivatives p-RC6H4N02 (R = Me, Cl) were reduced to the corresponding anilines with CO in aniline solution in the presence of NiX2L2
(X = Cl, Br; L = PR3, R = Me,Et,Ph) or
NiI2(PhNH2)4 as catalyst precursors at 150-180°C and 20 bar. The aniline solvent was simultaneously converted to diphenylurea [107]: RC6H4N02 + 3C0 + 2PhNH2
-
RC6H4NH2 + CO(NHPh)2 + 2C02
Nitrobenzene and para-substituted nitrobenzenes were reduced by CO with good yields to anilines in the presence of a Pd(OAc)2 + PPh3
(1:4) catalyst in aqueous AcOH. The analogous reduction of
PhN02 in BuOH + H2S04
(1:5) gave p-HOC6H4NH2 [1081.
7. Miscellaneous Reductive Transformationsof CO and CO2 The formation of MeOH from CO and H20 is catalyzed by Mo(C0)6 at temperatures below 15O'C
[1091. The reduction of CO or CO2 with Everitt's salt (K2Fe[Fe(CN)61) to methanol (see A.S. 1985 refs. 79,80) could be performed in a catalytic manner by reducing the Prussian blue (formed in the stoichiometric reaction) electrochemically and using for this a commercial solar cell as energy source [llO]. Electrocatalytic reduction of CO2 to MeOH at an Everitt's salt-mediated electrode in EtOH solution in the presence of 1,2-dihydroxybenzene-3,5-disulfonato
(tiron) ferrate(II1) has
been studied. The formation of an intermediate Fe(III)-tironethyl formate complex was established 11111. The reduction of CO2 to MeOH on Pt electrodes modified with Everitt's salt was studied in the presence of different Fe and Cr complexes as homogeneous catalysts. Highest current efficiency was achieved with [112]. Methyl formate coordinated to the metal [(H20)(C204)2Cr1was proposed as an intermediate [113]. Carbon monoxide and carbon dioxide were electrochemically reduced to MeOH in the presence of the following metal complexes 3as homogeneous catalysts: Fe(CN)5(H20) , [Cr(C204)2(H20)21-, CrC15(H20)2-, FeF5(H20)2-, Fe(CN)5(NH3)3-, and 4,5-dihydroxy-1,3benzenedisulfonatoiron(II1).
Best current efficiency was 100% for
CO and 16% for CO2 [114]. Controlled potential electrolysis of a DMF solution containing [Fe4S4(SCH2Ph)4]2- under CO2 resulted in the formation of formate and phenylacetate. In the presence of excess PhCH2SH the yield of phenylacetate increased and the cubane
References p. 5 14
420 structure
of the catalyst
was preserved
during
a longer
period
11151.
The homogeneous studied
with
Maximum
activity
photocatalytic
was
achieved
[116]. Carbon
complexes irradiation
with
light
electron
transfer
numbers
ligands were
in MeCN
as catalyst.
The effective
reduced
to formate
mediator
11181.
by Ni and Co complexes investigated.
[119]. Electropolymerized
catalyze
of
to colloid-associated
as electron
+ H20 was
under
composed
tris(bipyrazine)RuiII)
!bpz)3Ruf
Rh(bpy)3C13
of the two
to methane
system
was electrochemically
observed complex
t~~raaZaannUkne
donor,
from
as photocatalysts. ratio
be reduced
of CO2 to CO catalyzed
reduction
of macrocyclic over
could
in an aqueous
colloid
took place
i1171. Carbon dioxide co2 in aqueous solution using Cathodic
of CO2 to CO was
a 1:l molar
as electron
and a Ru metal
as senzitier,
with
dioxide
visible
triethanolamine
NaHC03,
reduction
5H20 and Re(C0)3(bpy)Cl
Rh(bpy)3C12.
the reduction
High
turn-
films of a
Ni
of CO2 to formate
[1201. Reaction formamide HCaONa
nf Et2NH
selectively
as additive
with
CO2 gives
tetraethylurea
PdC12(MeCN)2
already
+ Et2NH
co2
with
at room
-
as catalyst
temperature
Et2KNEt2
and diethyland PPh3 or
and 1 bar:
+ Et2NCH0
d This
is a reductive
pressure
III. Hydrogenation 1.
transformation
Catalytic sition-metal
and Reduction
H/D exchange
( 7 6-C6H6)Re(PPh3)2H C6D6
hydrogens
its metal-hydride
diation
of the trihydrides
in C6D6
solution
solvent,
with
the hydride
is promoted
at 200°C.
this process
catalyzes
and aromatic
and meta
exchange
in alcohols
(Zr, Nb, Ta) alkoxides
are the intermediatesof
ortho
H2 and high
D and T Labeling
H Exchange, -
between
of CO2 not using
[121].
hydrocarbons,
ligand
the H/D exchange
and between
ligands.
with
UV light
causes
C6D6
and the
The complex
the D source
( 3 5-C5Me5)RuH3(PR3)
ligands
compounds
[1221. The complex
if irradiated
of its PPh3
by early-tran-
Carbonyl
does
not
Irra-
(PR3 = PPrl3, PPh3)
H/D exchange
and the coordinated
[1231.
between
phosphine
the [124].
421
The soluble iridium polyhydride H5Ir(PPrij2 catalyzes the H/D exchange between C6D6 and CH4 in the presence of neohexene at 80°C. The deuteration of methane needs several days and is preceded by the conversion of all neohexene into neohexane and by H/D exchange between C6D6 and both the hydride ligands and all the hydrogens on the phosphine ligands [125]. See also [71.
2. Hydrogenation of Olefins a)
Fe, Ru, and OS catalysts
Hydrogenation of cyclohexene is catalyzed by [CpFe(C0)212 at 17OC and 6 bar with a turnover of 16 h-1. No mononuclear intermediates are formed during this reaction because if hydrogenation is performed with a mixture of [CpFe(C0)212 and Iq-C5Me5)Fe(C0)212 no mixed-ligand dinuclear complex can be found in the product [126]. The PhLi + Fe4S4C1i- (6:l) system catalyzes the hydrogenation of terminal double bonds of monoenes and dienes with H2 [127]. Partial hydrogenation of refined canola oil with Ru(PPh3)3C12 as catalyst was examined. This complex catalyst was about as effective as heterogeneous Ni catalysts in producing hydrogenated fats with a low trans-fatty acid content [1283. The bis(imido) clusters Ru~(NAIY)~(CO)~
(Ar = Ph, p-substituted phenyls) catalyze
the hydrogenation of olefins under 3 bar H2 at 98OC. The clusters probably remain intact during the catalytic cycle [1291. The anionic ruthenium cluster [Ru3( /J-NCO) (CO),,]- was shown to catalyze the hydrogenation of terminal, unactivated olefins. The analogous [HRU~(CO)~~]- cluster was inactive but catalysis could be promoted also by Cl- or Br- in place of NCO- [1301. The tetraruthenium clusters H4Ru4(C0)12 and H4Ru4(C0)10(PPh3)2 were anchored on polymer supports modified by tertiary phosphine groups and used as catalysts for the hydrogenation of 1-hexene [1311. Three types of Ru carbonyl complexes anchored to Si02 via phosphine ligands: H,Ru4(CO)8(PPh2C2H,-SIL)4,
Ru3(CO)g(PPh2C2H4-SIL)3, and RUG
(PPh2C2H4-SIL) were used as catalysts for the hydrogenation of ethene at 70°C. Decarbonylation of the anchored complexes occurred only above 18O'C [132].
References p. 5 14
422 The orthometalated lysts
for olefin
high:
it was equivalent
of
found
and superior
of O2 enhanced
amounts
ligand
into OPPh3
to be cata-
(22) was especially
to that of HRu(PPh3)3Cl
Small
one PPh3
(19-22) were Activity
hydrogenation.
that of Rh(PPh3)3Cl. transforming
complexes
to
its activity
by
[1331.
tOPhI
(OPW2 19
20
Pd [P(OPh)3lCl O,p’ tOPhI
22
21 Hydrogenation catalyzed numbers with
CpNiOs3(CL-H)3(CO)8L
lated
An allylic
from the reaction
See also
and 3,3-dimethyl
Dienes
were
clusters complex mixture
and 3 bar with hydrogenated
is
turnover
to monoenes
(L = CO, Ph2PH,
derived
butene
P(C6H4Me-o)3
from the diene
was iso-
11351.
[44, 187, 2031.
Co, Rh, and Ir Catalysts Selective
with
[134].
anhydride at 60-80°C
by OS~(NCO)(CO)~~ of 3-8/day
as catalysts.
b)
of maleic
hydrogenation
of citral
cyanoethylenediaminocobalt
Maleic
and
fumaric
dicarboxylic succinic
first
acid by vitamin
ing methyl
esters
way to methyl
catalyst
acid were
acid was
reduced reduced
B12s
of the three
succinate
to citronella1
[138].
in MeOH/H20
to succinic to fumaric
(cob(l)alamin) acids were
was achieved at 25'C
acid,
[1361.
acetylene-
acid and then to
11371. The correspond-
also
reduced
in a similar
423 The complexes
olefins
[139].
tene with
cyclohexene, genation
were
determined
labile
tion
of Me sorbate
earlier was
was
were
were
also
in the presence of the mixed
genated
the acrylic
carboxylic
acid
less active
complex
[143].
thus
system
saturated process
ketones
shown
systems
to catalyze
and esters
is both chemically
Rhodium(I) as catalyst
polymeric
quinoxaline-Rh hydrogenation
dienes complex
silica-supported
and the phosphines of E-toluenesulfonic hydrogenation
of alkenes
were
with
attained
active
than their
References p. 5 14
P/Rh
under ratios
homogeneous
of the
and RhC12(2-methylhydrogenacomplex
the cyclooctene
chloride
formed
in a two-phase
the hydrogenation
of
a,P
at the C=C bonds. controlled
-un-
The
[1441.
complexes
were
used
alkenes
and alkanes
[1451. A polyphenyl-
and used
found mild
to alkanes
as catalyst
and bromopropene
complexes
prepared
from
for the 11461. Ph(COD)(acac
(n = 1,3) in the presence
(Et0)3Si(CH2)nPPh2 acid were
the hydro-
[(C8H17)3NMel+[RhC141-
butyraldehyde Rh(1)
hydro-
of terminal
was prepared
of olefins,
involves
by transesterifi-
activity
phosphinocarborane
to monoenes
in acetone
liberating
than
selectively
[1411.
be per-
The allylrhodium
and diffusion
for the hydrogenation
and conjugated
Cationic
was
could
in the homogeneous
was examined.
ion pair
of Me
of Me sorbate
followed
substrate
was Me
Rh(CO)(PPh3)2C1
acids
11421. The catalytic
The solvated
product
as catalyst
from RhC13. 3H20 and methyltrioctylammonium liquid
Main
The mechanism
ligand
catalytic
Hydrogena-
the hydrogenation
acrylic
systems
Hydro-
to the
of Me trans-3-hexenoate
+ 2-alkylaminopyridine
olefins
[1401.
The complexes
catalyzed
+ 2-alkylaminopyridine
tion of different provided
amounts
of a base.
acid
127).
Rh(PPh3)3C1,
as catalysts.
anhydride
[RhCl(cycloocteneJ212 allyl)
at 100°C with
RhC1(PPh3)2(Ph2POCOCH=CMe2)
solution
with
in this case
substituted
genation
ref.
and this was attributed
for the hydrogenation
of highly
by using
of
formed.
which
inactive
has
that of the hydrogenation 1984,
of
of l-hep-
as catalyst
complex
studied
[Rh(NBD)(dpe)l(PF6)
Hydrogenation
hydrogenation
(see A.S.
faster
but significant
and Me hexanoate
cation
with
and HRh(CO)(PPh3)3
trans-2-hexenoate
formed
of homogeneous
dihydro-olefin
[Rh(NBD)C112,
2-amino-1,3,2-di-
for the hydrogenation
[DPPA = HN(CH2CH2PPh2)21
of 1-heptene
linoleate
as catalysts
and compared
more
and
used
The kinetics
Rh(DPPA)Cl
been determined
(L = different
[RhCl(CO)L12
oxaphosphorinanes)
to be efficient conditions.
Highest
of 2; such catalysts analogues
[147].
catalysts
for
activities
were more
424 Homogeneous and
hydrogenation
Ir(1) complexes
(E = P, As) was concluded plexes
that
of the terdentate
the enthalpies
step
of a ligating was
of formation
shown
show
group,
to direct
e.g.
show
olefin
(23) gave
effect
was
14-electron
this
of
!1451. The
of H 2 in case of as solvent onto
and CH2C12
the directing
only
group.
species
Thus,
for
This very pronounced
for the 12-electron
like Rh(PPh,),Cl
"IrL2"
did not
[149].
‘j-
23 [133,
com-
of activation
\c *
catalytic
selectivity
it was
on an olefinic
(24) in 99.9% yield.
characteristic
HO
See also
experiments
relationship
the addition
containing
system:
HN(CH2CH2EPh212
OH or COOMe
the face of the molecule
by Rh!I!
of the dihydride
an inverse
as catalyst
directing
ligands on kinetic
[Ir(COD)(PCy3)(py)j!PFUj
example,
catalyzed
(M = Rh I Ir) and the enthalpies
H2M(L)Cl
substrate
Based
investigated.
the rate-determining presence
of cyclohexene
24
216, 2171.
c) Ni, Pd, and Pt catalysts The reaction been
found
product
to be an active
hydrogenation
of alkenes
to the catalyst: took place
in their
on Pd(acacj2
was
nylpyridine)
were
catalysts
studied reduced
[151j.
only
in THF has
for catalytic
groups
were
stoichiometric
poisonous reduction
prepared
and used
active
catalysts
of Pd(I1)
or H2 and tested and acetylenic than Pd black
the same conditions
on phosphinated
for hydrogenation
based
poly(2qi-
as catalysts These
1152, 1531. catalyst
1,3- and
into cyclohexene
catalyst
with
alcohols.
on a polyaziridine-PdC12
disproportionated Pd(I1)
Complexes
by NaBH4
were more
was hydrogenated
A heterogenized was
catalyst Nitro
of hydrogenation
of olefinic
50°C and 5 bar H2. Under hexadienes
presence
of formation
for the hydrogenation
lohexene
homogeneous
and alkynes.
and LiA1H4
[150].
The mechanism
complex
of nickelocene
Cycat
1,4-cyclo-
and benzene
!154].
montmorillonite
of olefins
and acetylenes.
425 The results swelling
obtained
in various
properties
Polymer-supported
Pd(0)
and Pt(O)
reacting
CpPd( q3-C,H,)
and used
for the hydrogenation
catalysts
prepared
or Pt(COD)2
d)
1133, 135,
Other
catalysts
with
were
prepared
by
4,4'-diisocyanobiphenyl
found
lenes.
In some cases
phenylacetylene
into
Asymmetric -
specific
and alkynes.
The Pd
to the about
as active
Rh(I1)
moderately
can be observed:
into cyclooctene
containing
(R =CHOHPh)
hydrogenation
1,3-
and di-
[1571.
Addition
bridging
was
of prochiral was
observed
tested olefinic
for
acids.
Practimixture
but resulted
homogeneous
mandelate as catalyst
and the reaction
of PPh3 or chelating
the activity
enantioselective
and acety-
of Olefins
complex
no enantioselectivity
decreased
selectivities
Z?&$'Ph2
diolefins
1,2,3,4_tetraphenylbutane
[R~(oocR)~(H~o)]~
was not homogeneous.
the chelated
of olefins,
are transformed
Hydrogenation
The dimeric
the asymmetric
containing
the hydrogenation
and 1,5-cyclooctadienes
ficantly
the
Pd [1561.
complexes
catalyze
cally
with
Metals
Zirconium(II1)
ligands
in accord
1941.
moiety
3.
were [1551.
of alkenes
in this way were
as PdIC or polystyrene-bound See also
solvents
of montmorillonite
amines
signi-
in the formation
catalyst
of a
(0.~. up to 15%)
[158]. A practical l,l'-binaphthyls been
developed
synthesis (BINAPs,
of
(RI- or
(S)-2,2'-bis(diarylphosphino>-
25; Ar = Ph, p-MeC6H4,
ptBuC6H4)
[159].
PAr2 25 PAr2
References p. 5 14
25a
has
426 The degree
of asymmetric
(-)-methyl
esters
[Rh(dipamp)l+ of the
complexes
rnenthylgroup
butenoic ence
induction
acid
was
diphosphine
(-)-norphos were
dependent
were
from
The best
[1611.
Rh(I>-chiral
(90%) of the desired with
in the pres-
obtained
derivatives
(26) using
as catalysts.
(an artificial
(27) as ligand
with
and the ligand
derivatives
systems
L,L-enantiomer
(R)-prophos
x
acid
and L,D aspartame phosphine
01-acylamino-2-
and several
were
The dehydroaspartame
to L,L-
of
hydrogenated
results
by
on the configuration
[Rh(COD)Cl12
(Z)- a-acetylamino-2-butenoic (115)
and different
was obtained
ester
formed
ligands.
hydrogenated
yield
strongly
and its methyl
the substrate
of (+I- and catalyzed
The Z- and E-isomers
[160].
of in situ catalysts
chiral
in hydrogenation
of 3-hydroxy-2-methylenebutyrate
Pa/C
Highest sweetener:
11621.
I
COOMe
HOOC R =CHO
26,
or
The mono-dehydro different
chiral
COOCHZPh
Leu-enkephalin
Rh(1)
complexes
[Rh(dipamp)(COD)](BF4) 68%
CR)-product
product metric
leads to 93%
was obtained.
is mainly induction
in the substrate
controled
This
were
prepared
(S)-product shows
due to the two chiral
Application while
of the
and overcomes
aminoacids
using of
with Rh(BPPM)Cl
that chirality
by the catalyst
already
asympresent
[163].
’
CONH-CONH-CONH
The water
(28) was hydrogenated
as catalysts.
soluble from
chiral
the parent
in an aqueous-organic
“>lCO f .k
ditertiary compounds
two-phase
system
phosphines
COOMe
28
(29) and
(30)
by sulfonation
and used
for the asymmetric
hydro-
427 genation with
of
Rh(1)
ci-acetamido complexes
lower
than those
ganic
solvents;
cinnamic
acid and some of its derivatives Optical
as catalysts.
obtained
with
yields
the unsulfonated
the best value
was
were
somewhat
phosphines
in or-
88% [1641.
H PAr2
Ar =
PAr2 n=Oorl 30 The new chiral ligand Rh(1)
biphosphine
in the asymmetric complexes
analogue
hydrogenation
as catalyst.
(32) was prepared
metric
hydrogenation
plexes
as catalysts
(31) was prepared
Best
of dehydro
of dehydroamino
o.y. was
and used
and used
90%
as chiral
acids
[1651. ligand
N-acylaminoacids
as with
The DIOP in the asym-
with
Rh(1)
com-
11661. H Me2C
!
I0
P(C6H4Me-312
‘0 T
P(C6H4Me
-312
H 32
31 The water-soluble been prepared
and were
tion of dehydro strongly
chiral used
aminoacids
decreased
in water
was noted
chiral
[1671.
when
dipamp
(33) and
(34) have
in the asymmetric
or EtOH.
the enantioselectivity
no such effect liqands
diphosphines
as ligands
hydrogena-
Unexpectedly,
of these
or norphos
water
catalysts
while
(115) were used
PPh2 PPh2 H
33
References
p. 5 I4
34,
n = 16 or
42
as
428 The chiral cose
and used
phosphines
as ligands
for the asymmetric
cc-acetamidocinnamic
acid and
Phosphine
(35) gave
catalyst. than
(36) were
(35) and
itaconic
prepared
from D-glu-
hydrogenation
acid with
significantly
of
[Rh(COD)C112
higher
optical
as
yields
(36) [168].
The chiral as ligands with
bis(tertiary
The best amido
optical
cinnamic
of the type pared
[169].
as ligands
were
achieved
substrate:catalyst
R = CH2NH2
(37) and
of unsaturated
(38) were
carboxylic
used
acids
prepared
Several
(R = different
as catalysts
36,
in situ from [Rh(COD)Clj2. --(70%) was obtained in the case of d-acetbistertiary
In most
(up to 99.5%) could
phosphines
and acyl groups)
were
hydrogenation
acid derivatives
(PP = 39).
ratio
chiral
alkyl
in the asymmetric
cl-(acylamino)acrylic
complexes yields
yield
(39)
and used
ferent
complexes
acid
R =CN
phosphines)
in the hydrogenation
Rh(I)-phosphine
35,
with
cases
even under
be increased
of dif-
[Rh(COD)(PP) I+
very
high optical
pressure.
up till
pre-
The
50.000
[1701.
0 (men)2P (men)2
P
The water used
soluble
Rh(1)
for the hydrogenation
cinnamic and
0
acid
furnished
in water
complex
of the
solution.
(40) has been prepared
sodium
salt of
The catalyst
(S)-N-acetylphenylalanine
was highly
in 90% o.y.
(BF4 );
and
d -acetylaminoactive
11711.
40
429
Optical of
yields
up to 100% were
C(-acetylaminocinnamic
acid and
obtained
in the hydrogenation
its methyl
ester
in the presence
of Rh complexes
of 3,4-(R,R)-bis(diphenylphosphino)pyrrolidine,
bound
(41). The catalyst
to silica
could
be reused
three
times
[172].
Y p+
-O\
41
-NH-i&-Nx)Rh(COD)*
-07Si-fCH213 -0
H
The chiral were
prepared
olefins
tioselectivity itaconic
sugar diphenylphosphinite
and used
of prochiral
acid
Phq
as ligands
with
in the asymmetric
[Rh(COD)Cl12
was obtained
with
derivatives
(42) and
(43)
hydrogenation
as catalyst.
Complete
(43) in the hydrogenation
enan-
of
[1731.
X0
0
42 The air-stable starting
N-acyldehydro-
a-amino
in a catalyst
selectivity lost
than
its activity
bisphosphinites
and the cationic
as catalyst
Immobilizing
[1741.
resulted
chiral
from D-glucose
(L = 44a) was used
ed
43
acids.
Optical
yields
the homogeneous
catalyst.
of 94-99%
were
cation
showed
If recycled
R
achiev-
enantio-
it slowly
[1751.
R’
44 a
H
OPh
44 b
OMQ
H
44 c
OPh
H
of
exchanger
a better
but not its enantioselectivity
I
Rh(L)WD)+
hydrogenation
on an organic
is some cases
prepared
complex
for the asymmetric
this complex which
(44) were rhodium
A polymeric
phosphine
tetraethylenepentamine plexes
of this
lysts acid
was prepared
and the chiral
copolymer
with
for the asymmetric
NiCl2
from diethyl
tartrate,
bisphosphinite
and CoC12 were
hydrogenation
of
(45). Comused
as cata-
d -acetylaminocinnamic
[1761. ,COOEt
Ph2P0, CH
45
I Ph2PO The new chiral pared. lysts
Cationic
o.y.
92%)
‘COOEt
aminophosphine
Rh complexes
for the asymmetric
(highest 53%)
AH
phosphinites
of these
ligands
hydrogenation
(46-49) were were
used
of dehydroamino
[177] or of (50) to pantolactone
pre-
as cataacids
(51)
(best o.y.
[178].
Me -CH-0PPh2
,’ H
I
tH20pph2 CH-NPPh2
Ph-CH-NPPh2
c,, N I
I
I
I
R
R’
Me
Rh(1)
of dehydro
complexes used
‘i’
COOR
PPh2 49
51
of the chiral
as catalysts
amino
in some cases
n
48
50
(53) were
.’ .H
CH20PR2
PR2
47
46
H :
Ph2PO
acids.
Optical
the arsine
phosphines
and arsines
for the enantioselective
proved
yields
up to 94% were
to be the more
a
Ph’
,Ph E” E “’ Me
observed
selective
L1791. Me,
(52) and
hydrogenation
52,
E=P
53,
E= As
ligand
and
431 Asymmetric saturated SO-80°C
ketones
[180].
of cC,p -unsaturated
was achieved
and 40 bar
cyclobutene). rone
hydrogenation
with
Highest
o.y.
The chiral
for asymmetric
(62%) was obtained
Ru complexes
hydrogenation
o.y. was
26%
ing the enantiomers were
used
like
(56) or
at 23OC) 100%).
[1811.
of acetylated
The Ti complexes
yields
is useful
important
A-(R)-
ligand
the reaction
and optical
This new method
dehydroamino
for the asymmetric
and
styrene.
Highest
and catalysts acids.
Ru complexes
BINAP,
(54) and
hydrogenation was rather
were
generally
slow
bear-
(55), of enamides (2-6 days
excellent
(near
of various
[182].
A-
54
(58) and
as
used
for the synthesis
products
as catalysts Q-ethyl
at
in the case of pho-
The hexacoordinate
for the asymmetric
(57). Although
physiologically
as catalyst
~~Ru~(co)~[(-)-DIoP1~
(n = 2,3) were
of the chiral
as catalysts
chemical
trans-IIRuClL2
to
[L = trans-1,2-bis(diphenylphosphinomethy1)
Ru~(CO)~[OOC(CH~)~COO][(-)-DIOP]
Highest
ketones
(S)
(59) activated hydrogenation o.y. was
34%
with
- 55
BuLi were
of 2-ethyl
[183].
used
hexene-1
432
4.
Hydrogenation
of Dienes
Alkynetitanium
complexes
H2 and are catalyst Selective of PMe3 or
catalyze
Homogeneous
selective
fins,
dienes,
of olefins were
dienes
aldehydes
to unsaturated
from
BuMgBr
with
in the presence
(MeC5H4)2TiC12,
and LiA1(OBut)3H 11851.
The dinuclear
catalyzes
[1861.
the
Hydrogenation
and ketones,
Unsaturated
alcohols,
unsaturated
High selectivities
of dienes
aldehydes
of ole-
and hydroformylation
by HOsBr(CO)(PPh3)3.
in the hydrogenation
to alkenes.
obtained
react
of alkynes.
of COD at 50°C and 1 bar in the presence
is catalyzed
observed
alkynes
place
of cyclopentadiene
and conjugated alkynes,
takes
Ru~(COD)~(O~CCF~)~(H~O)
hydrogenation
of cyclooctene
systems
(n = O,l),
the hydrogenation complex
for the hydrogenation
to cis-olefins
(MeC5H4)2Ti(OPh)2_,Cln
Ru carboxylate
like Cp2Ti(PhCCPh)(PMe3)
precursors
hydrogenation [184].
and Alkynes
to monoenes
were
ketones
and of
hydrogenated
to saturated
mainly ketones
11871. Hydrogenation piperylene) gave was
of 4-methyl
using
K2;Co(CN)5]
4-methyl-2,6-nonadiene hydrogenated
Co(PPh3)3X products isomerized
to norbornene
different
CIDNP pair
(X = Cl,Br)
NBD dimers
[1891.
measurements, intermediate
by HCO(CO)~ both reactions
[190].
of
diamine)]
[188], Norbornadiene
and the tricycloheptane
to 2,4-dimethyl-1,3-pentadiene
2,4-dimethyl-2-pentene
(linear dimers
or K2[Co(CN)3(ethylene in 90% yield
+ BF3. Et20 catalysts were
nonatrienes
in 5-19%
(6Oj by yield.
Main
Tetramethylallene and hydrogenated
and HMn(C0)5. take place
is to
As supported
over
a common
by radical
433
al
60
Diphosphines
of the type
(n = 1,3) were
used
complexes
were
effective
octadiene
11911.
gave
complexes
which
were
active
with
tertiary
In some cases
(iBu)2AlH
[192].
from the ferrocenyl
thiother
ligand
catalyst
for the hydrogenation
octadiene
to cyclooctene
Several polymers
were
developed
Depending
be performed:
(depending
The catalysts tion
formed
was
found
of 1,3-cyclo-
[1931.
systems
based
on linear
or poly(ethyleneimine) hydrogenations
the following
as
in liquid
hydrogenations
could
on the ligand);
could
be separated
Ni - alkynes
to s-alkenes.
from the product
by ultrafiltra-
[194].
See also
5.
for selective
on the metal,
of acetyle-
Rh - aromatics (cyclohexanone from nhenol), suqars; nitro groups, C=N bonds, alkynes to -cis or trans
Pd - alkenes, alkenes
solution
amines
the resulting
(61) and K2PdC14
catalyst
like poly(vinylpyrrolidinone)
ligands phase.
in acetone
new homogeneous
of 1,3-cyclo-
The complex
to be a homogeneous
The
aliphatic
for the hydrogenation
to olefins.
with
on silica.
for hydrogenation
of PdC12
were
reduced
Rh complexes
catalysts
dienes
6’
SPri
(EtO)3Si(CH2),P(Ph)CH2CH2PPhZ
to immobilize
Reaction
nes or conjugated complexes
&
[146, 150, 156,
Hydrogenation
of Arenes
Hydrogenation 40-80°C
and 20-60
to cyclohexane
157, 2171.
of benzene bar
[195].
was carried
[196]. Naphthalene
and Heterocyclic
is catalyzed liquid-phase
out over
was hydrogenated
P.hC13.3H20 + methyltrioctylammonium in a two-liquid naphthalenes, mainly went
References
phase naphthols
system
partial
p. 5 I4
hydrogenolysis
by aqueous hydrogenation
rhodium
trichloride
Ru(OH)C13
chloride
(Aliquat
naphthoates
ring-chlorinated [1971. Phenol
were
at
of benzene at 20°C
at 30°C and 1 bar with
to give decalin-free
and ethyl
at the non-substituted
Compounds
a
336) catalyst
tetralin.
Methyl
hydrogenated
naphthalenes
was hydrogenated
underin the
434
presence
of catalysts
-soluble
polymers.
activated with
gave preferentially
complexes
and methyl
as catalysts proceeded
of poly(acrylic cyclohexanone
with
polyacrylic
acid,
methacrylate-maleic
for the hydrogenation
over
with wateracid)
(74%) along
[1981.
cyclohexanol Rhodium
on Rh and Pt complexes
the Rh complex
Thus,
by NaBH4
copolymer
based
furfuryl
alcohol
styrene-maleic
acid copolimer
of furfural.
acid
were
used
Hydrogenation
to tetrahydrofurfuryl
alcohol
[1991. See also
6.
[1941.
Hydrogenation
The anionic catalyze
of Carbonyl
group
6 carboxylates
the hydrogenation
50 bar. Activation anion-stabilized
Compounds
of dihydrogen dihydride
and ketones
was proposed
or dihydrogen
R
I HC -0::
(M = Cr,W,Mo)
M(C0)5(0Ac)-
of aldehydes
at 125OC and
to proceed
complex
,+, i ,;M(CO);
(62)
over
the
[ 2001.
62
‘..A ,’
AI
Acetaldehyde and
was hydrogenated
445 bar using
[HR~3(C0)1~1-
[HRu(CO)~~-
proved
A similar
was
in the synthesis
found
and 500 bar
[201].
as catalyst.
to be much
reaction.
activity
of methanol
Hydrogenation
investigated.
HCl the selectivity
with
complexes
RuC12[Ph2P(CH2)nPPh2]
catalysts
was
bar.
Linear
acetone
tested
olefins
could
be
saturated
were
from
99%
were
gas at 230°C
group
of citral
complexes
as cata-
[202]. The activity
hydrogenated
only with
for this
and in the presence
at 65-95OC but cyclic
the most to prooyl
reduced
of
of the
as hydrogenation
substrates
was hydrogenated
hydride
the two complexes
synthesis
Ru(II)-PPh3
(n = 1,2,3)
easily
or cinnamaldehyde aldehydes
was
different
hydrogenated
(n=3). Propionaldehyde tonaldehyde
with
between
solvents
CO + H2 at 180°C
as a catalyst
of the carbonyl
In protic
for dienol
with
The trinuclear
less active
difference
(3,7-dimethyl-2,6-octadienal) lystswas
to ethanol
active
and lo-17
olefins
and
catalyst
alcohol,
and cro-
to the corresponding
[203]. When -trans-4-tert-butylcyclohexanol
was
435 subjected
to 35 bar H2 at 145OC
amount
(63) in toluene,
cis
of
(25.2 mole
%) and trans
corresponding shows
that
alcohol described
(69.7 mole
cyclohexanone
(5.0 mole
(63) reversibly
dehydrogenation. as
in the presence
of a catalytic
a constant-composition
catalyzes Complex
mixture
%) alcohols
%) was formed. ketone
This
(AS 1985,
as the result
hydrogenation
(63) was earlier
[(?14-Ph4C4CO)(CO)2Ru]2
of the
as well
and
erroneously
ref.
97)
[204].
63
Hydrogenation use of several
of aldehydes
MX(OCOR')(CO)(PPh3)2
involving
involving ligand
at 150°C
HMX(CO)(PR3)2
Hydrogenation
of Ru(CO)~(PBU~)~(ACO)~
reaction
is performed
nium and
partly
carbonyl
in MeOH
transformed
homogeneous
Rh + MeI catalysts decarbonylation
or
pro-
species
or
for the carboxylate
[205].
oxalate
at 180°C
gives methyl
and 130 bar in the
glycolate.
If the
the glycolate
as solvent,
glycol
[206].
is subseThe ruthe-
(A~O)~R~~(CC)~(PBU~)~V (Aco)4Ru4(CC)8(PBu3)2~ were
hydrogenation
H4Ru4(CO)8(PBu3)4
were
active
equilibrium
into ethylene
carboxylates
(AcO)~RU(CO)~(PBU~)~
cursor
and 30 bar. Mechanisms
in the catalysis
of dimethyl
by the
R' = Me,Et,Cy,tBu,
as catalytically
presence
quently
R = Ph,Cy;
a bidentate-monodentate
as a key step
was achieved
of the type HMX(CO)(PR3)3
(X = Cl,Br;
CH2C1,CHC12, CF2C1,CF3) posed
and ketones
Ru and OS complexes
identified
of AcOH [207].
benzylic
to EtOAc
using
In the presence
carboxylic
and reduction
as intermediates
acids
by synthesis
in the
the catalyst
pre-
of Ru + MeI or
undergo
reduction,
gas at 220°C
or
and 430
bar:
Ph-+COOH
The ratio
__c
+ Ph-+I
of the two products
acid on the metal:
Referencesp. 514
Ph-+CH3
Ru generally
depends
favors
on the structure
reduction
of the
and Rh decar-
436 Benzoic
bonylation. tions with
[2081.
hand
if
(65) and the latter with
lactone
gave
(64) was compound
(67) was
to toluene
of the cyclic
the lactone
first
reduced
(66) in 99% yield. to the diol
in toluene
and benzalacetone
!reflux)
as H acceptor,
in 88% yield
obtained
such condi-
(64: at 160°C
by LiA1H4
the
[209].
6Me
bMe
64
under
anhydride
was dehydrogenated
as catalyst
H2Ru(PPh3)4
isomeric
is reduced
as catalyst
Ru2Clq(dppb)3
On the other
acid
Hydrogenation
67
bMe
OMe
65
The kinetics in py has been Co and showed
of hydrogenation
a maximum
with
Enantioselectivity catalyst enced
systems
used
by the addition
fects were
explained
Rh complexes ketones
dextrin
dextrin;
and stereoselectivity
of suitable
aldehydes
to give
active react
quantities
hydrocarbons
the favorable
effect
of
in
of Rh-phosphine could
These
12111. Aryl
[Rh(HD)C1j2 Yields
with and
ef-
alkyl H2 in p -cycle-
are much
or in the presence p -cyclodextrin
be influ-
or dihydrido
in THF solution
yields.
order
!2101.
as additives.
species
by Co(dqm)2
to be first
of monohydrido
of
in high
of any cyclodextrin
catalyzed
of ketones
bases
by the formation
of catalytic
in the absence
found
py concentration
for hydrogenation
as catalytically
and aromatic
the presence
of benzil
The rate was
determined.
of
lower
cl-cyclo-
is probably
due
437 to the fact that
it forms
D-(-)-Pantolactone metric from
hydrogenation [Rh(COD)C1]2
and BPPM
(68) were
asymmetric
hydrogenation
efficient
could
[213].
prepared
ligand
be achieved
with
was
as ligands 64-72% fluence
hydrogenation complexes
R=
68b,
R = -CONHPh
68c,
R=
center
[iPr2P(CH2)4PPri]
-COOBut
the chiral a-amino
R‘ = Me,
;
PCY2
)
References
p. 5 I4
of hydrogenation
(benzylideneacetone prepared
drastically
of phosphine
12151.
PCY2
PCY2 71b
The selectivity
excess
6%
PhCH2
XT- 0 _.-
71 a
phosphines
if an achiral
R’
0
PCY2
catalysts
no in-
70
o-..
complex
(70) in
the o.y. was only
69
Ph
(71)
RkHCONHkHCOOMe * t
-
*
esters
had almost
of the reaction:
was used,
esters
phosphines
of the substrate
OH
7’COOMe RCOCONHCH
compounds
The
MeS02-
of N- (a-ketoacyl)-a-amino
containing
N-( a-hydroxyacyl)-
The chiral
R = Me,
as catalysts.
92% enantioselectivity
68a,
on the diastereoselectivity
diphosphine
for the same
[214].
produced
o.y.
in situ -pyrrolidinebis-
as ligands
complexes
[2121.
by the asym-
formed
The new chiral
Rh(1)
A Rh(1)
yield
the catalyst
(68~) with which
PPh2
Asymmetric
the substrate
in 92-98%
and used
CYZP,
(69) with
with
of (50) using
phosphines
most
a complex
(51) was prepared
of cC,p -unsaturated
or cinnamaldehyde)
with
in situ from [Ir(COD)(OMe)12 -changed with the P/Ir ratio. When
was used,
carbonyl
Ir-phosphine and a twofold
the C=C bond was hydrogenated,
with
438
a P/Ir
ratio
selectivity
of 10 the carbonyl 12161.
the hydrogenation hyde
The Ir(II1)
of phenylacetylene
to hydrocinnamaldehyde
See also
[218].
alkenes
benzothiazoline
!219].
is catalyzed
nitro
groups
are not hydrogenated
genation
catalysts;
the best
of 4-vinylpyridine
PhMeCHNH2
gave
was
with
12221.
The Mo(VI)
com-
using
Hydro-
Pd com-
increased of the
by photochemical
grafting
hydrogena-
of PdC12
+ !S)-
(72b) containing
hydrolysis
72a,
R
72 b,
R = NH2
transformed
N02 HCI
2231.
Hydrogenations complexes
[ (MeCP)Mo( I-L-S) (P-SH) I, for the hydrogenation at room
[2201.
for E-C1C6H4NH2
q
by H2
and nitrile
[2211. Asymmetric
Acidic
of
at ambient
compounds
Complexing
HCl the amine
(72b) into L-lysine
Miscellaneous
investigated
was obtained
in 11% excess.
was pre-
isoquinoline)
carbonyl
as catalysts.
its L-(-Jenantiomer
1101, 194,
nitro
(72a) in the presence
workup
The com-
to be the most
the same conditions
onto polyethylene
after
found
in DMF solution
and selectivity
support
for the hydro-
for the hydrogenation
Formyl,
under
tion of 3-nitrocaprolactam
strates
[217:.
pressure.
(L = quinoline,
supports
activity,
was
of aromatic
of p-nitrochlorobenzene
the stability,
as catalysts
at elevated
compounds
DMF solution.
on polymeric
used
catalyst
by trans-PdC12L2
in alkaline
8.
at 60°C
[Rh2C12(COD!2(phenazine)l
Hydrogenation
plexes
See also
100%
and of cinnamalde-
alcohol
as ligand
complex
as homogeneous
and aromatic
conditions
were
to aniline
The Rh(1)
and used
plexes
almost
catalyzed
Compounds
0x0 complexes
of nitrobenzene
containing
pared
to styrene
and cinnamyl
of Nitro
Rhenium(V) genation plex
with
[Ir(phen)C12jCl
[19,44,146,178,187,194,199,492].
7. Hydrogenation
active
group was reduced complex
[(MeCp)Mo( u-S)12S2CH2 could
be used
of a series
temperature
and
as homogeneous
catalysts
of nitrogen-containing
and 2-3 bar.
Phenyl
aside
subwas convert-
439
ed to aniline,
azo compounds
phenylhydroxylamines hydrazine.
The C=N double
isocyanates
were
is uncertain dimerized
to hydrazines,
to anilines, bonds
in imines,
also hydrogenated.
as catalyst
[H3Ru4(CO)121of the catalyst
to the corresponding
precursor
at 120°C
formamides
-
The role
R
I R = Me, Et, nPr
a
a
74
The olefinic + CoC12)
hydrogenated
sultam-imide
(75) was
and catalytically
to give
discrimination selectivity
and 50 bar.
of the isocyanates
R/N\C/N\C/H
73
(LiA1H4
of
[224].
I
+ H2
be reductively
H2 in the presence
the hydrogenation
and
of the reaction
(73) could
H ZR-N=C=O
isothiocyanates
(74) with
is probably
and
to 1,2-diphenyl-
The mechanism
[2231. N-Alkylisocyanates
to N-formylureas
nitrobenzenes
azoxybenzene
(76) and
favored
(77). In all cases
the formation
was obtained
with
stoichiometrically
[Ir(COD)(PCy3)]+PFi
of
or Pd/C
diastereoface
(76); highest
the heterogeneous
diastereo-
catalytic
system
[225].
4
Pr
76
I\ ‘H
Na
inepr
+
502
75 The chiral (78) with Optical
References
purity
p. 5 I4
glycine
(79) was prepared
D 2 in the presence of the product
of catalytic was about
by the hydrogenolysis PdC12 80%
in D20/TKF
[226].
of
at 25OC.
440
H
Ph coo-
_ 0 Br
79
78 Uranium
hydride
PhN02
to azoxy-
PhPh,
and Ph3AsO of added
UH3 reduces
to Ph3As
in boiling
and the sensitivity synthetic
reagent i194,
towards
oxygen
also
9.
Dehydrogenation Cycloalkanes
were
dehydrogenated
for these
secondary
or allylic
aldehydes
was achieved
R R’
+
with
hydrogen
_
Ruthenium
ally1
complexes
cycle
1229 I.
with
energy
under
of
Cc ,p -unsaturated
as catalyst
R
proposed
0
z
and ally1
conversion
+ C3Hfj
as intermediates
photoirratiation.
in all cases;
+ co2
of iPrOH
Ir, Rh, Pt, and Ru complexes
than unit
"photo-thermal
were
Dehydrogenation
SnC12. 2H20 as catalyst was higher
or
acceptor:
-0COOMe
catalytic
unsaturation
Dehydrogenation
to ketones
H2Ru(PPh3)4
and arenes
by
coordinative
[2281.
R’
investigated
substrates UH3 as a
to cycloalkenes catalytically
Multiple
reactions
alcohols
as
carbonate
OH
do not recommend
and in some cases
iH21r~Me2C0~,~PPh3~,1~Sb~6)'
t
in the absence
organic
1971.
stoichiometrically
methyl
against
to PhH and to azobenzene,
12271.
See
was necessary
azoxybenzene
THF or at 130-170°C
The low reactivity
solvent.
(X = Cl,Br,I)
PhX
and azobenzene,
efficiency"
combined
efficiency
(iridium)
was
was
with
Quantum
in one case
of the
to acetone
larger
even
the
than one
[2301. Dehydrogenation 200°C
by the black
and AlEt3.
of tetralin solid
The catalyst
to naphthalene
formed
from CoCO3
contains
tetraline
is catalyzed
(suspended
at
in tetralin)
and naphthalene
which
441 from
can be extracted
it with
is catalytically
inactive.
hanced
Rh(PPh3)3C1
alone
by adding [231].
Et20;
The activity which,
The Co porphyrins
the dehydrogenation
the residue
of the system
however,
(80) were
of hydroquinone
of this
can be en-
is inactive
tested
extraction
with AlM3
as catalysts
for
[233].
80 R = Me,
Et
R’= H, Me, OMe, N02,
diols
Dehydrogenation
of unsymmetrically
is catalyzed
by Ru- or Rh-phosphine
ence
of H-acceptors
nant
products
tuted
are
[235] were
catalysts.
Using
induction
could
in the pres-
ketones.
The predomi-
y -1actones
(82), respectively. found
(81) and 7 -substi-
H2Ru(PPh3)4
to be the most
the corresponding be achieved
1,4- and 1,5-
complexes
O:,p -unsaturated
p-substituted
6 -1actones
HRh(PPh3)4
like
substituted
NMe2
[234] and
active
complexes
and selective
of DIOP
some optical
[234-2361. Me
OH
Me
OH
0
81
c 0 Me
Me Me
Me OH OH
Primary simultaneous
-
and secondary ligation
Dehydrogenation from amine
References p. 5 I4
amines
react
with
and dehydrogenation
2 (P)Fe(III)Cl+ 5 RNH2 -
transfer
a2
Fe(II1)
porphyrins
(P = porphyrin
ligand):
2 (P)Fe(II)(H@2 + R'CH=NH+ 2 m$l-
starts nitrogen
by reversible
outer-sphere
to the porphyrin
ring.
by
electron
The reaction
442 models
the monoamine
See also
1209,
10. Hydrogen
a)
239,
ne-2
of
transfer
resulted
No photoreaction Transfer
by iPrOH
triene
2-cyclohexene-l-01 HCo[PPh(OEt),]4
also
is methyl
under
hexene-1
linoleate
or hexe-
to methyl
linoleate
which
is transformed
H-transfer
is catalyzed
The active
of
by
catalyst
of free phosphonite
Some
as solvent,
in n-octane
Intramolecular
irradiation.
Addition
in a cyclo-
and H4Ru4(C0)12.
to give cyclohexanone
HCo[PPh(OEt)2]3.
[2371.
of cyclohexane
with
of methyl
place
[239].
light
in the formation
by RUDER
takes
the H-donor
into a conjugated
with
was observed
hydrogenation
is catalyzed
hydrogenation
in this case
P-450
bonds
(Bu4N)4[Pt2(P205H2)41
+ iPrOH mixture
[2381.
oleate
of cytochrome
Reactions
of C=C or C-C
Irradiation
and acetone.
function
2431.
Transfer
Hydrogenation
hexene
oxidase
is
decreases
conversion
[240]. Hydrogen-transfer achieved
with
solution
at 13OOC.
were
Methyl
the products.
of ammonium tative
yield
from methanol
Ru-phosphine
complexes formate,
If the reaction
acetate, according
to diphenyl-acetylene as catalysts trans-stilbene
was carried
hexamethylenetetramine to the following
was
in toluene and bibenzyl
out in the presence
was
formed
in quanti-
equation:
+ 3 PhCH2CH2Ph 3 PhC2Ph + 6 MeOH + 4 MeCCXXG14-
+ 6 H20 + 4MeCOSH
The formation result
of trapping
of methanol
of hexamethylenetetramine of formaldehyde
dehydrogenation
[241].
formed
was obviously as the primary
the product
443
b)
Hydrogenation Various
of C=O bonds
p-benzoquinones
to the corresponding lyst
in very
by iPrOH phenone
and 1,4-naphthoquinones
hydroquinones
good yields
C2421.
and dehydrogenation is catalyzed
suitable
by iPrOH with
Transfer
by Cp2ZrH2
The method
of primary
as cata-
of ketones
by benzaldehyde
at 130°C.
reduced
Zr(OH)20
hydrogenation
of alcohols
for the dehydrogenation
were
or benzo-
is especially
alcohols
to aldehydes
[243]. Alkyl using from
aryl ketones
iPrOH
hydrogenated
[244].
were
as H donor tuted
hydrogenation
and
[Rh(NBD)L2]+
The rate
increased
nation
synthesized
with
Optical
by iPrOH
yield
was
with
was
investi-
electron-donating
prop-
2,2'-bipyridines
in the transfer
in the presence
15% in the best
iPrOH
(L = p-substi-
of iPrONa
The new chiral as ligands
achieved
and ketones
as catalysts
increasing
[245].
and used
of acetophenone
as catalyst.
up to 75% were
in the presence
of the substituents
(83) were
yields
of aldehydes complexes
triphenylphosphines)
gated.
alcohols
and an -in situ Rh catalyst formed methionine sulfoxide, and KOH. Reac-
low but optical
Transfer
to benzylic
source
[Rh(l,5-hexadiene)C112,
tion rates
erty
were
as hydrogen
hydroge-
of [Rh(COD)C112
case
[2461.
(S)-EtMeCH
-
,-pF= (S)-PhMeCH
-
83 Asymmetric is catalyzed DIOP,
prophos
vated
by first
especially
hydrogen
(27), and chiraphos. treating
optical
(58%) was achieved [247].
When
achieved
[248].
dppp)
References p. 5 I4
from iPrOH
depend
have
catalytic
on activation
time.
catalyst
to be acti-
activity
and
Highest
0.~.
and acetophenone
in situ from Ir(COD)(acac) and the -P(men)2Ph and P(nmen)Ph2 proved to be active transfer
reaction
was used,
The complexes used
The catalysts KOH;
ketones
diphosphines
formed
acetophenone
were
to prochiral
of the chiral
an Ir/prophos
in the hydrogen
ketones.
dppe,
with
P(men)Ph2,
catalysts
them with
yield
The complexes
phosphines
transfer
by Rh and Ir complexes
optical
HIr(COD)L2
as catalysts
from
iPrOH
yields
(L = PPh3,
for the transfer
to prochiral
up to 42% were AsPh3;
L2 =
hydrogenation
444 of cyclohexanone like KOH were
c)
using
iPrOH,
not necessary
Hydrogenolysis
EtOH or MeOH
as H-donors.
for catalytic
by Hydrogen
activity
Cocatalysts
12491.
Transfer
See [2291.
11. Reduction a)
without
Transition
Metal
The binuclear lene
(85) which
rhodium
hydride
reactions
formation
(84) hydrogenates
shows
CIDNP
which
of the metal-centered
is the active
Ph2P-
Hydrogen
Hydrides
This
to styrene.
the reversible
Molecular
hydrogenating
agent
biradical
85
84 Low Valent
Transition
Unsaturated
the saturated substrates -OH group
Metal
dicarboxylic
to give
CP2Ti(CO)2
Ti(II1)
carboxylic
proved
PPh2
1 1 H ARh(CO)2 (CO)Rh* 1 I’H Ph2P,,PPh2
1 ,H, 1 (CO)Rh -Rh(CO) 1 ‘H’ i Ph2Pv PPh2
b)
by
isomer
12501.
Ph2P -
PPh2
phenylacety-
was explained
that
Complexes (e.g. maleic
acids
carboxylato
acid.
complexes
Experiments
the hydrogen
acid)
react
with
(86) containing
with deuterium-labeled
source
is the carboxylic
acid
[2511.
2Cp2Ti(CO)2
H\
+ HOOC ,c=c\
/H
COOH
0
-
Cp2Ti(
0 )C-CH2-CH2-C((
)TiCp2
0
0 86
Reduction p-hydroxy
ketones
to the carbonyl of reduction of ketones
of
c(,p -epoxy
group
probably [252].
ketones
in good yields. but
(e.g. 87) with
Stereochemistry
is lost at the
resembles
a.-position.
that of dissolving
SmI2 yields
is retained
p
The mechanism
metal
reductions
445 0 0
0 -
87
Functionalized vinyloxiranes like (88) have been found to undergo facile reductive epoxide ring opening with SmI2 in THF in the presence of a proton source to provide (E)-allylic alcohols (89). The reactions take place already at -9OOC and yields above 70% can be achieved in most cases [253].
R=COOEt,
CN, COMe
R 88
89
Several a-ketocarboxylic
acids and u -dicarbonyl compounds
were reduced by TiC13 to the corresponding a -hydroxycarboxylic acids and a -hydroxyketones, respectively [2541. Tricyclic epoxides like (90) were successfully deoxygenated to the corresponding olefins (91) in a one-step procedure using 2 equivalents of WC16 in refluxing THF [255].
OAc
-
OAc
The bifunctional complex [Co(salen)Na(THF)] promotes the reductive coupling of methyl pyruvate (92) to dimethyl dimethyltartrate (93) and of p-tolylcarbodiimide
(94) to tetra-E-tolyl-
oxalamide (95); the reductant is transformed into Co(salen) [2561.
References
p. 5 14
446
TH3
p -
2 MeCOCOOMe
MeOOC-C-C-COOMe AH bH
92
/-\ u-
.N=C=N
CH3eN=C-NHeCH3 CH3 CH3oN=!-NH+H3 95
94 Reduction
of substituted
gave pyrroles, PhCH=CHN02
could
ing oximes
mined
be reduced
Fe3(C0)12 good
c)
ArCH2CR=NOH
by CrC12
The biphasic
and HBF4
yields
in aqueous
with
reduced
in benzene
aqueous
by
12581. The 4was deter-
[Fe(CN)6!
of benzylic
afforded
Tic13 Thus
to the correspond-
15-17"s yields
of bromamine-T reduction
with
divinylamines.
THF to 3,4_diphenylpyrrole
were
ArCH=CRN02
of the reduction
[2591.
nitrostyrenes
and in some cases
oximes,
j2571. Arylnitroalkenes
kinetics
g3
thiols
desulfurized
with
products
in
[260].
Inorganic
Reductants
in the Presence
of Transition
Metal
Complexes The epoxide (97) by WC16
(96) was deoxygenated
+ BuLi
in refluxing
to the corresponding
THF with
98% yield
alkene
[261].
Me$o&oAc Me&&OAc
96 The Fe-S
cluster
the reduction nBuLi
formed
used
instead
(98) acts as an electron
of S-phenyl
and PhLi
ucts
97
thiobenzoate
to give benzil
from the
and benzoin
substrates
of the cluster,
transfer
and phenyl along
with
and the reductants.
practically
agent
benzoate
only these
coupling If FeCl
in
with prodwas
3 coupling prod-
447
ucts were formed [262].
PhS.
PhS’
98
The activity of the complex reducing agent obtained from tBuOH, NaH and Ni acetate could be significantly increased for the reduction of olefinic double bonds by the addition of Me3SiCl [263]. The reagent prepared from tBuOH, NaH, PPh3, and Ni acetate in an etheral solvent was found to be very effective for the reductive coupling of heteroaromatic halides (99, R' and R" = = H, Me, MeO, C4H4). Chlorides or bromides were better than iodides which often led to significant amounts of reduced byproducts (100) [2641.
R’ /
I3
x
R" ‘N
100
99
Reduction of alkyl and aryl halides by iPrMgBr, KBH4 or LiA1H4 is catalyzed by Ti complexes. A catalyst system containing Cp2TiC12 and iPrMgBr was found to be the most effective 12651. The nitrogenase iron center model compound (Et4N)4tFe6Sg(SCH2CH20H)Cll was prepared and its catalytic activity for the reduction of acetylene to ethene by KBH4 determined [2661. Reduction of acetylenes to olefins was performed by NaBK4 in the presence of FeC12 and dihydrolipoamide
(101) or a similar dithiol as catalyst sys-
tems. Best results were obtained with a catalyst containing equimolar amounts of Fe(I1) and dithiol. Hydrogen transfer probably took place within an iron-dithiol-acetylene complex and NaBH4 served to regenerate the starting complex [267].
m(CH2)4coNH2
SH References p. 5 14
SH
101
448 The mechanism and assisted ined
(reduction
found
that
acted
Rh(OEP)Cl
tion of aryl of other
found
d
The analogous
aliphatic
mild
or
nitro
+ [B02]-
groups
in MeOH
for the reduc-
in the presence
system
the deuterated
cycle,
and NaBH4
reagent
If the Cu 2+/NaBD4
reductants
re-
by Rh(TPP)Cl
of the catalytic
[269]. Copper(I1)
akcohol
as a black
12683. Aerobic
2 R2CH-OH
of cinnamaldehyde,
exam-
it was
stoichiometry:
to be an efficient,
the deuterated
formed
in THF is catalyzed
is borane
or LiAlH4 cases
halides)
catalyst
is an intermediate
functionalities.
produced.
(or aluminide)
NaBH4
and tertiary
with NaBH4
In the three
or alkyl
to the following
hydride
the reduction
nished
with
reductant
was
boride
+ [BH~I- + O2
A rhodium the actual
alkenes
as a heterogeneous
according
2 R2C=0
performed
investigated.
of nitriles,
of ketones
solution
was
the cobalt
precipitate duction
of reductions
by CoC12
was used
alcohol
for
(102) was
Ni2+/[BD4]- and Co2+/[BD4]-fur-
(103) under
such conditions
[270].
D /
phwCHo
102
CHDOH
.b Ph
103 D Diisobutylaluminium compounds
to saturated
has now been from MeLi tivity
found
unsaturated
(105)
Reduction
support
reduces compounds
that the addition
reagent.
carbonyl
by Pd(PPh3)4 propenes
carbonyl
and CuI) dramatically
of this
compounds
hydride
if
of MeCu
increases
The new reducing
compounds
ti,p -unsaturated
[104] to
HMPA
(prepared
the activity system p,u
carbonyl
is present.
It
in situ -and selec-
transforrnes doubly
-unsaturated
carbonyl
[271].
of
(E)-1,3-dichloropropene
and yields
only
(the Z and E isomers an allylpalladium
by Bu3SnH
two of the three
of 1-chloropropene-1).
complex
is catalyzed
possible
as intermediate
l-chloroThe results
[272]. Applying
449
the same method
for the reduction
l,l-dichlorobutadiene case
an oxidative
product
addition-
and a Pd(I1)
the catalytic acid media
species
cycle
of technetium
Reduction
by NH4Tc04.
is probably
Octene-1
was proposed of Pd(I1)
[273].
is catalyzed
as the only product.
p-elimination
Reduction
for the reaction.
of 1,1,1,4-tetrachlorobut-2-ene,
was observed
Tc(V)
is transformed
process
of methylene
blue
The catalytically
into octane
in MeOH
in the absence
of hypophosphite
place
Propargylic
acetates
by Sm12
in the presence
yielded
allenes
cases
in
form
is present. which
aqueous No hydroappar-
[275].
(106) were
of Pd(PPh3)4
exclusively:
of set-acetates
formed
by SnC12 active
containing
genation
as the H donor
completes
[274].
if KH2P02
takes
pathway
by Bu3SnH
or Rh(PPh3)3C1
serves
to the
as the probable
to Pd(0)
KOH and Ru(PPh3)3C12
ently
In this
leading
reduced
to allenes
as catalyst.
allene-selectivity
and from primary
acetates
and alkynes
tert-Acetates
was decreased mainly
alkynes
in were
[276].
OAc R--z--;-R”
I
-
Rj-.=(R’+ R-&q H’
‘R’
’I
R
106
See also
d)
12251.
Reduction
via Silylation
The homogeneous none monosilyl in refluxing
ethers benzene
reductive (107) was
found
[277!.
+ HSiR3
References p. 5 14
silylation
-
of quinones
to be catalyzed
to hydroquiby
X-&'Ph3)3Cl
450 d ,p -Unsaturated duced
ketones
at the olefinic
comprised
double
of Pd(PPh3)4,
-unsaturated
Ph2SiH2
carboxylic
the same conditions
and aldehydes
bond using and
Several
and aminophosphine-phosphinites the asymmetric complexes.
the product
nyl ethanol. and
Highest
chiral
(CL-naphthyl)PhSiH?
very
of
d ,p -
sluggish
tested
under (108:
as ligands
catalyzed
of the catalyst
re-
system
aminophosphinites
of acetophenone
and measuring
o.y.
selectively
The reduction
was
(109) were
hydrosilylation
Enantioselectivity
hydrolyzing
ZnC12.
acid derivatives
[2781.
were
a three-component
in
by Rh
was determined
the optical
purity
(43%) was obta ined with
after
of
CL-phe-
the ligand
(110)
12791. H
n/ Ph2PO
n/
NH
Ph2 PO
NPPh2 PPh2
108 Reductive Tic14
cleavage
+ Et3SiH.
the acetal reduction
The reaction
(111) could
‘* Alkyl
aryl
of
(-)-norphos
group
chemoselective:
with
for example, 112) without
[280].
in the presence
could
prochiral
[R~(NBD)c~]~
be
to undergo
of Rh(I)-phosphine
used
ketoximes
amines
hydrosilylacatalysts.
on hydrolysis
for the reduction
and -in situ catalyst systems phosphine like (-)-DIOP or
inductions
cat? -
and
of oximes
and a chiral
(115), optical
+ Ph2SiH2
shown
(114) yielded
t2811.
ioH
was performed
into the ether
(113) were
silylamines
Using
is highly
be transformed
ketoximes
accordinly this method
composed
to ethers
COOEt
Ph2SiH2
The resulting
amines.
of acetals
of the ester
tion with
110
109
up to 36% were
achieved
to
451 e)
Organic Reductants in the Presence of Transition Metals The use of 80% aqueous formic acid for enantioselective
transfer hydrogenation of N-acyl dehydroaminoacids using Rh(I) complexes of the ligands norphos (115), prophos (27), DIOP, and (116) was described. Addition of HCOONa increased the optical induction which in some cases exceeded the values obtainable with H2 [282]. H PPh2
‘NMe2
*z
t-Y
4
&_
PPh2
PPh2
(- ) - norphos
115 ;
116
The reduction of phenylglyoxalate
Me
(-)-
BPPFA
(117) to give methyl mande-
late by the NADH model compounds (118) or (119) is catalyzed by Lewis acids. Using chiral europium
p-diketonates
(shift reagents)
as Lewis acids optical yields up to 55% were achieved [2831.
PhCOCOOMe
-
PhC?HCOOMe dH
117
COOMe
CONH2
Me H
CH2F’h 118
119
The epoxides (120) were transformed into the hydroxy alkenoates (121) by stereospecific hydrogenolysis with ammonium formate catalyzed by Pd(O)-phosphine complexes. Yields were around 80% [2841.
Me
120
Referencesp. 514
R
R’
H
Et
Me
121
452 1,2-Dienes
(123) were
sis of alkynyl
carbonates
by Pd2L3.CHC13
+ PBu3
the dienes
were
prepared
by the selective
(122) with
ammonium
(L = dibenzylideneacetone)
reduced
to alkanes
hydrogenoly-
formate
catalyzed
at 30°C. At 65OC
[2851.
OCOOMe RA
* or OCOOMe
&-
R’
123
122 The hydrogenating system
(AS 1985,
Pd on carbon. reduction
activity
ref.
This new combined
of nitro
groups
(olefins,
ketones
(124),
an analog
of rubredoxin
anilines
nitro
conditions
complex
The ion pair chloride
catalyst
was
formed
shown
could
and after
again
transformed chlorides
sites,
to N-aryl
functional
[286].
Complex
catalyzes
the reduc-
hydroxylamines
addition
and
acetates
used
could
olefins
active
system,
salt could
species
be reduced
by using
to 1-methylnaphthalene
be
[2881.
water-soluble catalysts
took place
in the reduction with
of
by aqueous
crown-functionalized
as liqands
The
by addition
ammonium
and phase-transfer The reaction
from poly-
and acid chlorides.
of the quaternary
system.
In a similar
methylnaphthalene
olefins
transfer
in the form of NaRhC14
as chemical
(125) were
[2871.
the hydrogen
into the catalytically and ally1
two-phase
[2891.
phosphines
in situ
to acetylenes,
to the corresponding complexes
tane-water phase
of many
halides)
of
the selective
from RhC13. 3H20 and methyltrioctylannnonium
to catalyze
be recovered
Ally1
phine
active
compounds
(124) is formed
methylhydrosiloxane
HCOONa
and aromatic
by the addition
enabled
by o-xylene- cl,c(-dithiol. The reduction can also be by using FeC12 and Et4NC1 as catalyst since under such
achieved
NaC104
be increased reagent
in the presence
groups
tion of aromatic
of the HCOOH/Et3N/Ru(PPh3)3C12
274) could
formate
Pd phos in a hep-
in the aqueous triarylof l-chlorosalts,
cata-
453 lyzed
In this case the reaction
by Pd complexes.
in the organic
phase
was taking
[290].
n=l,Z
125;
Reductive halides
(hydroqenolysis)
dehaloqenation
was achieved
hydrosiloxane
or sodium
formate
Unsaturated
functional
olefins,
and ketones
were
[2911.
Phenol
as catalyst
by Pd(PPh3)$
solvent.
tions
place
as hydrogen groups
could
be selectively
aryl triflates
Et3N
of Pd(OAc)2
in the presence
these
functional
groups
and olefins
were
to tolerate
in MeCN/Me2S0 aldehydes, reaction
deoxygenated
(126) with
formic
and a tertiary
Unsaturated
found
donor
like nitro,
found to tolerate
of the corresponding
of organic
and polymethyl-
(X) like nitro,
by reduction acid and
aromatic
ketones,
the reaction
condi-
phosphine.
esters,
conditions
well
12921.
126
f)
Electroreduction
and Photoreduction
Electrochemical formed
with
electrode
reduction
a (Bu4N)3[Mo2Fe6S8(SPh)91-modified
in water
Hg electrode.
or with
Ammonia,
ry amines
were
was far more
cystine
formed.
a significant
The system efficient
catalytic
and improved
non-functionalized
the same complex
hydrazine,
electrode showed
of HOCH2CH2N3
current
aliphatic
In the case of secondary
References p. 5 I4
was per-
glassy-carbon in MeOH/THF
with
N2, and the corresponding based
[294]. Functionalized
were
and with
or tertiary
Co(TPP-OMe-E)
on the electroreduction
efficiency halides
a prima-
on the glassy-carbon
[293]. Heat-treated
effect
ced in DMF or N-methylpyrrolidone
and MeN3
electrochemically Ni(bpy)Br2
halides,alkanes
of or redu-
as Catalyst. and alkenes
454 were
the main
into dimeric
Water-soluble used
to catalyze
light
ic activity
cyaninato)
polymer-supported
to be a better (MV2+)
complexes
to MV'+
in methanol. [298].
IV.
Oxidation
1.
Catalytic with
cyclohexane
system
showed
catalyt-
for the reduction
Ru(bpy)<+
ions
the photoreduction yields
of Hydrocarbons
by ozone-air
with
84-89%
and. Cr(V1)
using
decrease
(Lu, Er, Y, of methylvioin the stated
or Hydrocarbon
of alkanes
in the presence
were
Groups
out with oxygen
.
5 as catalyst
superoxide.
for hydroperoxides
oxygen
Ketones
as 49% were
in the presence
of Ni(st)2
and carbonyl
of carboxylic
acid
b)
of Olefins
of Cr(C0)6
in the system
form of reduced
as high
salts of Co, Cr, and [2991. Oxidation
at low conversions.
present
was carried
yields
Oxidation
and polymetal was examined
selectivity
Fe30(0Ac)6py3
is probably
coulombic
in the product
[3001.
of
gave cycloCr(III), Hydroxylation
in CF3COOH
+ py as
and a cathode
as reduc-
in this electrochemical were
the main
attained resulted compounds
products
[301,3021. in hiqh
selectivi-
and. a hiqher
or Alkynes
of 2-alkenyl
and 4-alkenyl-di-tert-butylphenols
by Co(salpr)
leads
of oxygen
the side chain
corresponding
carbonyl
(129),
selectively
to the incorporation
and thus to the formation
compounds
oxygen
content
[303].
Oxidation
into
and
Oxidation
(127) promoted
derivative
of
[297!. Biscphthalo-
lanthanoid(II1)
quantum
of paraffins
The active
tant.
ties
Relative
of individual
of cycloalkanes solvent
were
by visible
of Alkanes
The effect
Cr(IV),
viologen
02
Mn on oxidation
hexanone
mainly
phthalocyanines
photocatalyst
of several
Oxidation
Oxidation
a)
metal
of methyl
than
Gd, Eu, Sm, Nd, and La) catalyze logen
transformed
The Ru(II)-tris(1,4,5,8_tetraazophenanthrene)
[2961.
order
were
The Ni and Cu complexes
solution.
proved
methylviologen
halides
[2951.
the photoreduction
in aqueous
dication
primary
products; products
(128). In the case
is incorporated
both
of the
of the alkynyl
into the side chain
455 (product
130) and into the ortho
position
(product
131)
[304].
R
OH
127a
128a OH
OH
R
A0
127b
128b
tl 129 The cleavage bony1
compounds
Rh(PPh3)3C1. solution
The reaction
diene-1,4-dione Some Ph3P0
molecule
of olefins
is catalyzed
at the double by several
requires
[305]. Homocooxyqenation
that both
occurs
is also 0 atoms
formed.
air oxidation
(LL = dppe
of olefins.
terminal
Formation
olefins
concentrations
labeling
containing
alkenes
yielded
of O2 in
give cyclooctaas catalyst. showed
to the same diene bidentate
were used
of ketones
linear
mainly
to
experiments
are transferred
Rh complexes
e.g.
of RhC1(PPh3)302
or Ph2P(CH2)2SPh)
reaction in the case of terminal and branched
enhanced
Isotopic
in the complex
bond by O2 to give car-
Rh complexes,
of COD by O2
in the presence
[306]. Cationic
[R~(LL)~BF~
Referencesp. 5 14
131
130
liqands
to catalyze
the
was the predominant while
products
cycloolefins of allylic
Some epoxidation
oxidation. neous
oxidation
of octene-1
or Pd(I1)
species
octene-1.
Oxidation
of oxidizable mediates
isotopically
became
Hydrido
catalytic
complexes
[3071.
catalyzed
labeled only
were
Homoge-
by Rh(II1) 02 and
in the presence
supposed
as inter-
13081. of cyclopentene
solvent
by PdCl2
ethylacetamide)2].
formed
from a palladium
is probably
[3091.
of ethene
to vinyl
ketone
acetate
is catalyzed by
is produced
by one mole
in turn,
which
derives
as a catalyst
than the analogous
02; the may be
its H from
[Pd,,l(phen)801(PF6)60
active
in
[PdC12(N,N-di-
hydroperoxide
which,
cluster
to be more
effectively,
a palladium
hydride
The giant
and found
to cyclopentanone
or, more
One mole
species
pared
using
of olefin
active
ethanol
in all cases
by 02 or tBuOOH
was studied
alcohols.
Oxidation ethanol
occurred
was pre-
in the oxidation iPdgG1(phen)60!(OAC)180
[3101. Aldehydes of 1-alkenes
tem
the major
air using
and a tertiary
cuc12, cuc12
were with
or the tertiary
of alkene
alcohol
were
vatives
(133) in about were
not formed
that comprises
omitted
(PdC12,
(132) yielded
vatives
of the catalytic
No aldehydes
alcohol.
[311]. Wacker-oxidation
stereomers
products
a catalyst
40% yield.
CuCl, the
were
terminal
no chloride of chloride,
134
sys-
The isomeric
benzoyl
phenylacetyl
derideri-
mF’h 133
oxidation
of 3,3-dimethyl-4-pentenoates
under
Wacker-conditions
in the reaction
the corresponding
COOR
either
from the catalyst
corresponding
-
was achieved
was present
when
02, H20) of the two dia-
132 Selective
formed
13121.
&p, (134, R = Me,Et)
oxidation (MeCN)2WClNO2,
methyl
mixture.
ketones
j-ooR
AcO
in AcOH
if
In the presence
were
obtained
[313].
451 Olefins were oxidized to ketones by 02, PdC12, CuC12, and water using a cyclodextrin to transfer the organic molecules into the aqueous phase. The relative reactivity of cyclodextrins as phase transfer agents for the oxidation of 1-decene to 2-decanone was
[314]. Based on the unexpectedly high trans P'a'Y influence of the OH- ligand it was proposed that the rate-deter-
mining step of the Wacker-oxidation of ethene is the attack of H20 on PdC12(0H)(C2H4)-
[3151.
See also [364].
c)
Spoxidation of Olefins The reaction of singlet oxygen with alkenes in the presence
of Ti alkoxides was employed to prepare epoxy alcohols. If diethyl tartrate was used as chiral auxiliary the reaction could be performed with high enantioselectivity; e.g. in the case of (135) the (S)-enantiomer of (136) was formed in 72% o.y. [3161.
02 /TPP/hv OH
Ti(OBd)4/(+)-DET 135
136
Olefins could be epoxidized by O2 in the presence of Mn(TPP)Cl, 1-Me-imidazole (as axial base), and benzoic anhydride if electrolytic reduction was applied. Faradaic efficiency of the system was 56% which is high if compared to analogous systems using chemical reductants [3171. The catalytic system composed of the NADH analogue (137), flavin mononucleotide
(138), N-methyl-
imidazole, Mn(tetraphenylporphyrintetrasulfonate) anhydride
and benzoic
(or benzoic acid) was found to be a highly efficient
catalyst for the epoxidation of olefins with 02. Any systemlacking one of the components did not show activity: if Mn was replaced by Fe the activity was much lower. Significantly, the structure of each component is very close to that of the native P-450 system [3181.
References p. 5 14
458
CONH2
Me
Air
oxidation
furnished
0
137
of norbornene
as the main
product
138
catalyzed
by
(MeCN)2PdCl(N0)2
exo-epoxynorbornene
concentrations
and a tetrahydrofuran
concentrations
[319].
(139) at low
derivative
(140) at high
&--4P” +q$-y H 139 See also
d)
[307,
3461.
Oxidation
of Aromatics
Aromatic
hydrocarbons
artificial
P-450
were
type catalytic
N-methylimidazole, creased
colloidal
the overall
as catalyst
was determined
for the formation The formation
coal during studied. tion
The results
of alkyl
groups
system
number with
hydroxylated
consisting
of HCl in-
conditions
were
concerning
sample
opti-
[321]. acids
of Ru04 as catalyst
provided information the coal
of oxida-
of Mn(st)2
(C2-C6) monocarboxylic
in the presence
by the
(TPP)MnCl,
02 in the presence
and the reaction
within
of
[320]. The kinetics
of the dihydroperoxide
of volatile
oxidation
effectively
Pt, 02 and H2. Addition
turnover
tion of m-diisopropylbenzene
mized
140
from
was
the distribu-
[322].
460 The reduction the catalytic CO(OAC)~
of CO(OAC)~
oxidation
+ NaBr
by xylene
of xylene
catalyst
with
[334]. The complex
and chloro-substituted
alkylaromatic
NMR.
that
It could
oxidation decreasing
be shown
of these
compounds
of the complexes
studied
as part
formation
compounds
the catalytic
alkylaromatic
stability
was
O2 in the presence
with
[335].
between
has been
activity
CoBr2
studied
of CoBr2
O2 increases
Oxidation
of
of a
by
in the with
of ethvl-
461
HyH20
-- 02
Me
Me 141
142 --,CH
-CHO
\o’
A heterogeneous-homogeneous the oxidation
of anthracene
of Ag ketenide See also
a) Oxidation
of Alcohols
of O-containing
The heteropolyacids anchored
H3[PMo120401
of iPrOH
the Ze-reduced
conditions
at 30°C.
[345].
chloride
by O2
was
diols
[343].
suggested
were
of ally1
investigated found
below
involves
and reoxidation
under
of
of cyclohexanol complexes each
in sub-
the reaction
by O2 catalyzed
in the pH range and above
as cata-
in aceto-
which
first order
alcohol
O2
and used
and Ru(III)-EDTA
EtOH was not oxidized
with
Photocatalytic
[344]. The kinetics
by Ru(II1)
was acrolein
were
by (Bu~N)~(W~~O~~)
was
The reactions
were
Groups
H4[SiMo120401,
by the decatungstate
Oxidation
kinetics
of oxidation 2.5
species
and catalyst.
Ru(II1)
A mechanism
by O2 catalyzed
studied
reaction
of primary
of the substrate
oxidation
Functional
H6[C0W~204~],
by O2 catalyzed
was studied.
oxidation
strate
for
by 02 in the presence
to poly(4-vinylpyridine)
for the oxidation
oxidation
was
to anthraquinone
[304].
Oxidation
nitrile
was demonstrated
[3421.
2. Catalytic
lysts
143
mechanism
by
l-3. Different
pH 2.0. The product
at pH 1.5 and glycidaldehyde
(143) at pH
[346]. The reactivity
plexes
toward
of coordinated
H abstraction
from Co to 02. Low electron the same time associated References
p. 5 14
dioxygen
is controlled transfer
with
in CoL4(B)(02)
by electron
enhances
low affinity
reactivity
toward
com-
transfer but is at
02. These
two
462 effects
determine
the oxidation
the catalytic
of secondary
activity
alcohols
of 2-ethylhexanol
by O2 in the presence
mainly
by the reactions
determined
and the 2-ethylhexanal ethanol
in the presence
is the abstraction
of PPh3.
PPh3
P(OMe)3
of racemic were
substrate
used
1-phenylethanol
used
were
is oxidized
(144) were
as axial
oxidized
kinetic
resolution
tivity
was obtained
as catalysts
rates
The giant
Pd cluster
subsequently
(144~)
Oxidation catalyzed gands
of alcohols
by Cu(1)
complexes
and counteranions.
the order
4,4'-Me2bpy
able product
was
Cu(I1)
complex
phatic
alcohols
found
R,
;
R = OMe,
144c
R = H,
;
Effectivity
with
to aldehydes
to partial enantioselec-
H R’=H R’
q
Me
the oxida-
the aldehydes
are
[3511. or ketones using
with
O2 and
different
of the complexes
li-
decreased
in
and Cl- > Br- > I-. No detect-
imidazole
(145) was shown
PPh3 or of the
catalyzes
investigated
> bpy > phen
R’=
144 b ;
to aldehydes was
Co(I1)
for the oxi-
Best
or ketones:
into esters
which
[350].
Pd561phen60(OAc)180
by O2 to aldehydes
transformed
leading
alcohol.
144a
tion of alcohols
by H202 to OPPh3
The two enantiomers
at different
PPh3 and
step
[3491. The chiral
by O2 to acetophenone;
ligands.
of the unconverted with
is catalyzed
The rate-determining
of the catalyst
dation
of a -phenyl-
atom by the 02 coordinated
leads
complexes
is
the substrate
{and H202 as byproduct)
to co. In a side reaction
Schiff-base
with
13481. Oxidation
of the a -hydrogen
to the deactivation
for
of Co 2-ethylhexanoate
of Co(II1)
intermediate
by O2 to acetophenone
by Co(salen)
of such complexes
13471. The rate of oxidation
or py as ligand
to catalyze
[3521.
the oxidation
by 02 in the presence
of KOH
The
of ali[3531.
463 b)
Oxidation
of Phenols
The reaction
of Mo(3,5-tBu2-catecholato)3
3,5-di-tBu-1,2-benzoquinone reaction
constitutes
the oxidation
According tures,
complexes
complexes
(dissolved
oxygen process
probably
atoms were
proceeds
was
of (146) by O2 in
(149)
in situ from FeC13
studied.
The reaction
complex,
and incorporation
and
mix-
of pyri-
semiquinonato-Fe(I1)
formed
by ring opening.
(148),
a series
of the reaction
via
complex
of a catecholate
accompanied
through
O2 in the presence
[3551. Oxygenation
intermediates
(147),
spectra
with
in THF) and the ligands
by the formation
This
describing
[354].
of an Fe(III)-bpy-py
to form peroxide
02 gives
scheme
O2 to benzoquinone
of catechols
as intermediates
the presence
ceeded
with
MO complexes
to EXR and Moessbauer
the oxidation
dineiron(III)
one step of the reaction
of catechol
of well-characterized
with
and Mo202(3,5-tBu2-catecholato)4.
Final
reaction
pro-
with
O2
of one of the products
of this
[356].
0
152
Oxidation various
Co, and Mn with lysts.
of
catalyst
(150) with systems.
the multidentate
The Cu,Co,
and Mn complexes
of the corresponding
References p. 5 I4
O2 was
studied
Thus the binuclear
benzoquinone
ligand
in the presence complexes
(151) were
promoted but with
of
of Fe,Cu,
tested
the selective
as cataformation
the iron complex
also
464 the
lactone
quinone
in a nonaqueous
[358] and catalyst
phase
[CuCl(p~)]~ the byproduct
-Co(acac)2-02
complex
the Cu catalyst could
formation
base
was
peroxo
of phenols
complexes
was
of di-,
studied
to be water
and
of a catechol-
could
be observed
step.
and the
of the o-quinone. The was proposed as the rate-
complex
to quinones
investigated
tri-,
in different
of Co(salen)
solvents
in the case of o-cresol
by Co-Schiff 13601. Oxi-
to p-quinones
and other
No reaction
as catalysts.
used
by O2 catalyzed
and tetramethylphenols
in the presence
base complexes conditions
found
step.
Oxidation
dation
was
for the preparation
of a dinuclear
-determining
Co(acac!2
to be the rate-determininq
no ring cleavage
be used
using
In the case of the Co
The decomposition
was assumed
to the corresponding
investigated
of the oxidation
be detected.
reaction
has been
[359] as catalysts.
no H202 could
With
[357]. Oxidation
(152) was formed
Co!II)
was observed [361].
Thymol
by O2 Schiff
under
the
(153),
carvacrol
(154) and o- and m-cresol were oxidized with O2 and Co as catalyst to the corresponding p-benzoquinones with high
salen yields
13621.
Me
Me
3 Q
OH
OH iPr
iPr
153 The Co(II) catalysts
Schiff
154 base
corresponding
better
their
stability
(155) were
of 2,6_dimethylphenol
p-benzoquinone.
than that of the analogous complexes
complexes
for the oxidation
Although
their
oxidative
to be usefu
by O2 to the
activity
ethylenediamine-derived against
found
was lower
Schiff
decomposition
[363]. Me Me
Me Me
t-t R=H,OMe
base was
465 Oxidation with
of isoeugenol
O2 and the Co(II)
the reaction
was about
as byproduct
[364].
(156) to vanillin
complex
(157) was performed
(159) as catalyst.
Selectivity
75% and dehydroisoeugenol
(158) was
of
formed
156 158
The direct lyzed
by Cu(1)
air oxidation and Cu(II)
some of the catalyst ating
ligands
enhance
for oxidation hydroquinone the latter complexes and
tested
were
exhibited
nuclear catechol
were more
N-ethylated
followed
p. 5 I4
active
complexes
membranes
Cu(I1)
containing
Mononuclear
of the Cu(I1)
Catalytic
and aqueous
to of
base of
(150)
pyrrolic complexes
of (150) and diof 4-methylcomplex
of
in the oxidation
of
oxidation
of alginate-Cu(I1)
a Michaelis-Menten
Schiff
in the oxidation
activity
[3671.
in the presence
preparation
for the air oxidation
poly(4-vinylpyridine)
was studied
from Na-alginate
one-pot
reactivity.
used
of benzoquinone
for the oxidation
The catalytic
hydroquinone
References
active
[366].
was performed
tions
In general,
Binucle-
The Cu catalysts
and dinuclear
as catalysts
complexes
partially
formation.
is cata-
solvents:
> 90% selectivity.
a convenient
the highest
found to be more
aprotic
the hydrogenation
[365]. Mononuclear were
to p-benzoquinone
in polar
achieve
o-quinone
affording
4-methylcatechol.
residue
systems
also catalyse thus
of phenol
complexes
solutions
type kinetics
of hydroquincne
membranes
prepared
of CuC12.
Oxida-
[3681. Oxidation
of
(160) to
lyzed
has been
were
(162, polyphenylene
complexes
active,
a DMAP:Cu
ratio
by 02 and cata-
the most
that
both mono-
active
species
mixture
product
95%
increased
the yield
(DMAP)
and dinuclear
beinq
Cu(DMAP)4Cl(OH).
of 4:1, Cl- as the counter-ion
OH- to the reaction (162) above
oxide)
of 4-(N,N-dimethylamino)pyridine
It was concluded
studied.
complexes Using
(161) and
by Cu(I1)
and addinq
of the desired
[369].
Me
Me
162
160
cl
Oxidation
of Aldehydes
Oxidation with
of propionaldehyde
Co acetate
found
as catalyst
to be 1.5 order
catalyst
and Ketones
[3701.
into perpropionic
in acetone
in aldehyde
The redox
+ EtOAc
and 0.5 order
properties
presence
d)
was
in O2 and
with their like
role
isobutyric
in cataacid or
of cyclohexanone
with O2 in the
of Cr(II1)
or Co(I1)
naphthenate
successively
1,2-cyclohexanedione, acid anhydride
[330, 331,
Miscellaneous The catalytic
the oxidation
13731.
gave
E-caprolactone,
2-hyadipic
[372].
3321.
Oxidations activity
of oxalic
rate was observed HCl
each
Oxidation
and adipic
See also
as solvent
[371j.
droxycyclohexanone, acid,
by 02
of l2-molybdophosphates
were studied in connection MxH3-xPMo12040 lyzing the oxidation of organic compounds methacrolein
acid
of Fe
2+
phthalocyanine
acid was studied.
derivatives
The highest
in the case of Fe-phthalocyanine
oxidation
treated
with
for
467 The kinetics
of oxidation
by RuC13. nH20 or different plexes
has been
the stability
these
An inverse
studied.
and catalytic
The rate of oxidation latter
of ascorbic
relationship
activity
which
acid com-
was
of the Ru(II1)
did not depend
catalysts
acid by 02 catalyzed
Ru(III)-aminopolycarboxylic
found between chelates
on 02 concentration
act as oxidase
models
[3741.
with
in this
reaction
[3751. Oxidation
of sodium
oxalate
with
phthalocyanine.2py)adduct
as catalyst
of a histamine-containing
polymer
dation
of ascorbic
Michaelis-Menten ascorbic
saturation
hibit
oscillatory
regime
were
specified
liquid-phase even
small
oxidation copper
amine
See also
13711.
Catalytic
The amount
sharply
oxygenolysis
inhibitor
Organic
shown
on the addition
by Fe, Co, Cu or Mn phthalocyanines. inhibits
by
Compounds of
by O2 in the presence of Na2C03
Addition
[3821.
The
(165) is cataof py or imid-
+
COMa NH2
NHCHO
164
of
Diisooctyl-
[3831.
COMa
p. 5 I4
in the
in the presence
(163) to (164) and
lyzed
Rcfcrcnces
to ex-
peroxide-initiated
in the oxidation
azole
163
of
of tetra-
13811.
to N-methylsuccinimide
the reaction
a
of CU(OAC)~
as inhibitors.
byproducts
of 3-methylindole
was
was studied
of N-containing
increased
showed
by 02 is decreased
The dicumyl
amines
activity
in the oxi-
of the oscillatory
The activity
esters
aromatic
a(Co
Oxidation
of the Cu complex
[380].
of polymeric
N-methylpyrrolidone of KMn04
3791.
was an efficient
Oxidation
[377].
of Me isobutyrate
of water
different
The catalyst
The conditions
of pentaerythritol
using
diphenyl
3.
[378,
oxidation amounts
complex
tetraazacyclohexadecine
character.
using
[3761. The catalytic
behavior
acid by O2 in the presence
benzo[l,5,9,13][b,f,j,n]
studied
latex-Cu(II)
acid was examined.
type
02 was
165
468 of Et3N by O2 to Et2NH
The oxidation by a Ru(III)-EDTA reaction
was
Anilines derivatives carbon too
studied
in MeOH
and MeCHO
in situ. --
is catalyzed
The kinetics
of the
13841. by O2 and Co(salen)
at reflux
temperature.
isocyanates
or urethanes
of aromatic
ketone
as catalyst
to azo
In the presence and ureas
of
are formed
3861.
Oxygenation Co(salen) benzoate
prepared
are oxidized
monoxide,
[385,
complex
as catalyst derivatives
of methylimidazole
in MeOH
hydrazones
resulted
and aromatic as additive
ketones
diazo
(166) using
in the formation [387].In
compounds
of methyl
the presence
(167) were
formed
[388].
//
X
X
X
yOMe
+
!I
0
X = H,Cl, NO2
166
R = H,Me,Ph,COPh N2 167
The binuclear catalyst diamine inact ive
Co(II)-Schiff
for the oxidation with
(168) was used
as
of N,N,N',N' ,-tetramethyl-p-phenylene-
Oz. The analogous
[389].
base complex
mononuclear
complex
was practically
469
Hydrazobenzene Co(salen)
was oxidized
by 02 into azobenzene
(169) or its bis(3-methoxy,)
A mechanism proposed
involving
a complex
derivative
of substrate,
using
(170) as catalyst..
catalyst,
and 02 was
[390].
n
The Cu(I1)
complexes
phenylpyrazole
of 1-methyl-3,5_diphenylpyrazole
could
be used
as catalysts
of 1-methyl-3,5_diphenylpyrazoline Oxidation in MeCN (171)
of o-phenylene solution
diamine
yielded
or 3,5-di-
for the dehydrogenation
in the presence with
the protonated
of 02
[3911.
air in the presence
of Cu
2,3_diaminophenazine
2+
cation
[3921.
Oxidation catalyzed
of N-benzylidine-o-phenylenediamines in pyridine furnished different
by CuCl
ing on the substituents group.
In most
obtained imidazoles coupling
of the amino
p. 5 I4
ring
caused
the E-methoxy
groups
cyclization derivative
to the diazo
O2
depend-
in the benzylidene
2,2'-diaryl-l,l'-bibenzimidazoles
substitution
(174) and with
[3931.
References
cases
but ortho
of the benzene
(172) with products
compound
(173) were to 2-arylbenzonly
oxidative
(175) was
found
470
R,R‘=H
172 QJ~=CH-p-@
175 R=H R’ = OMQ
II
Indolines [CuCl(py)&as selective
(176) were catalyst
oxidized
in CH2C12
to indoles
(177) with
O2 using
solution.
The reaction
was rather
(up to 92%) and no ring cleavage
was observed
[3941.
i-R2
-
H
H 177
176 Autoxidation cu(11).
Reaction
ternary
complex
mediate
which
the products
of diaminouracils products between
reacts [395].
(178) is strongly
are H202 and imines
diaminouracil,
with
an ionic
Cu(I1)
two-electron
catalyzed
(179). Probably
by a
and O2 is the intermechanism
to give
471
178
See also
4.
[402].
Catalytic
Oxidation
The Fe(I1) catalyst
of P- or S- Containing
complex
Fe(OPPh3)4(13)2
for the oxidation
p -peroxo
complex
[Ru(EDTA)(PPh3)1202
The rate-determining
complex
Ru=O(EDTA)(PPh3) in the oxidation
function
of L. Best yields
as axial
ligand
garded
and
7 bar in MeOH
Oxidation
Co(I1)
hexylamine
overall [402].
studied
as a
process
is strongly
of Ce(IV)
at 25OC
silica
via
complexes
with
rate was controlled
coordinated
by the proceeds
reaction
is catalyzed
by Co(I1)
a bond with
of O2 and CU(OAC)~.~H~O
species
re-
useful
were
found
and yields with
probably
to of
cyclo-
as catalyst
(180) were
thiolate
by the reoxidation
py. The
was
of 2-mercaptobenzthiazole
active
were
Oxidation
of bis(salicylal-o-phenylenediamine) active [4011. The kinetics, selectivity
in the presence
with
[3991. Aut-
accelerated
salts.
and is a synthetically
condensation
wzre excel-
synthesized)
in the catalytic
to amorphous
The catalytically
hexylamine
(TPP)Co(No2)(L)
to sulfoxides
give N-cyclohexylbenzothiazole-2-sulphenamide gated.
of
L = 4-cyanopyridine
complex
the oxidative
as an inter-
The all-trans-RuX2(SR2)2
separately
of EtSH to Et2S2
anchored
be the most
the
of the ruthenyl
by O2 was
with
of thioethers
solution.
amount
13 bar O2 at 100°C
[4001.
to Ph3PO
to sulfoxides
of a catalytic
complexes
identified
activity
achieved
13961.
as catalyst
(X = Cl,Br,SnC13,SCN)
(which were
of sulfides
addition
were
RuX2(Me2S0)4
as key-intermediates
oxidation
under
of Ph3P
for the oxidation
complexes
(Me2SO)2
was
to act as a
[398].
The complexes
O2 at 105OC
found
Compounds
by O2 in MeCN
step is the formation
[397]. Catalytic
complexes
lent catalysts
was
to Ph3PO
of PPh3 by O2 and Ru(III)-EDTA
In the oxidation
mediate.
of Ph3P
Organic
to
investi-
Cu-cyclo-
ligands of Cu(I)
and the to Cu(II)
4’12
+ II2
H2N
+
02
-
a&S-NH0 + H20
180
The kinetics Mn(I1)
of oxidation
iminodiacetate
of cysteine
immobilized
presence
of iron phosphate
See also
[306].
5.
a)
Catalytic
Oxidation
Inorganic
Oxidants
02 in the presence
complexes
of Organic
14041 was
Compounds
of
[4031, and in the studied.
with
Organic
or
General The high valent
were prepared active
acceptor
H202
Mn complexes
by oxidizing
species
are able to transfer
mation
of active
Ru(PPh3)3C12 tate.
[406].
of organic
systems
substrates
Oxidation Oxidation
tions
compounds
gave
by
in dry aceto-
for peroxidases,
catalases
was obtained
and
for the forfrom RuC13
and
and phenyliodosoace-
for the oxidation
or Hydrocarbon with
anthraquinone
groups
could
(181) were
(182) were proposed
tBuOOH
of a vide
variety
Groups
in the presence
in 97-100%
be oxidized
in dichloromethane
chromate
and FeC13
[405!.
compounds
[407].
of anthracene
methylene
by tBuOOH
the cyclic
be used
of Hydrocarbons
acetylacetonate Benzylic
may
system
organic
N-oxide
These
to any good oxygen
(metal 0x0 species)
N-methylmorpholine
(TMPjMn(OjBr
or NaOBr.
(TMPjMnX/NaOCl
evidence
intermediates
with
These
as models
Spectral
and
NaOCl
of different
of Fe(MeCN)4(C104)2
were'investigated
monooxygenases
with
one 0 atom
in the
and dehydrogenation
in the presence
nitrile
(TMPjMn(OjC1
(TMP)MnCl
and act as catalysts
Oxygenation
b)
with
on Silochrome
solution
yield
into carbonyl if small
used as catalyst. as intermediates
of Mo(V1)
at 40°C
[4081.
func-
amounts
of
tert-Butylperoxy [4091.
473
181
Oxidation been
of styrene
investigated
catalyst
with
182
to phenylacetaldehyde
by two cytochrome
NaOCl
as oxidant
P-450
and Fe(PFP)Cl
kis(pentafluorophenyl)porphyrinato]. is a primary
product
styrene
oxide
ketones
were
Mn(TDCPP)Cl MeCN
[410].
as the catalyst
as solvent. [411].
has been
demonstrated
porphyrins
Shape
selectivity group
with
also
er degree. those
various
for some
chain mechanism phenol
ionol
Oxidation under
and
was
of alkanes
hindered
metallogood regio-
at the least
hindered
were
oxideand
could
studied.
be completely
to or better
than
of
(183) as catalyst
With
t-butyl
of peroxide
iron
to a less-
[412]. Oxidation
complex
cyclohexenyl
The formation which
was
although
comparable
enzymes
the Mn(II1)
as cocatalyst
The corresponding
selectivity,
cyclohexene peroxide
involved
inhibited
as
were
a free radical by the hindered
[413].
of benzene
air has been
It was concluded,
References D. 5 14
tBuOOH,
cyclohexene
the two products.
agent
as oxidant
as catalyst.
good primary
w -hydroxylase
with
and py or imidazole substrate
into a!.cohols and
of imidazo1.e and in
sterically
for hydroxylation
acetate
showed
olefins
of
of the catalyst
iodosobenzene
The regioselectivities
found
the aldehyde
for the hydroxylation
very
With
[PFP = tetra-
that
[5,10,15,20-tetrakis(2',4',6'-triphenylphenyl)
porphyrinato)-Mn(II1) complexes
degradation
by using
was observed
of alkanes
has
Mn(TPP)Cl
from isomerization
in the presence
selectivity
as catalysts.
+ C6F510
H202 as an oxidizing
No significant
observed
methyl
High conversions by using
systems:
It was shown
and does not result
obtained
and epoxide
model
to phenol
investigated that oxygen
and benzoquinone
using
isotopic
is included
with
tracer
from both
H202+Fe
techniques.
sources
into
2+
474
the reaction
products
the process (H202, NaI04,
PhIO,
Fe(III)-bleomycin under
anaerobic
explained
and that
i413a;. Oxidation
and cumene
leads
deactivation
complex
the oxidation catalyst
with
was encapsulated
form as catalyst
Two types
benzene.
in the oxidation increased
lyst was
cumene
acetamides
selectivity
in competition
by NaI04
Cycloolefins and
RuC13.xH20
were
obtained
were
in MeCN/Ac20
were
oxidized
as catalyst with
oxidized
to the corresponding
two-phase
system
ternary
ammonium
was hydride kinetics
in which
with
NaOCl
salts
as oxidant
as catalysts.
abstraction
by phenyliodosoacetate zero order substrate
with
but zero order
acids
acids
respect
to both
oxidant
of C2-C4
olefins
with
[419].
NaOCl
results of glutaric
derivatives
were
in > 90% yield
and both
Initial
were
with
Best
case the yield
oxidation
or Pb(OAcj4
2
in
of Fe(C104j3
system.
Ru salts
in a
and qua-
step of the reaction
by Ru04 from the methyl
of the Ru(III)-catalyzed
at position
as cata-
benzene
carboxylic
and
of Fe(S04j2
in the presence
[420]. Methyl-substituted
cyclohexane
cyclododecane
to dicarboxylic
cyclopentene
82%
by iodoso-
to the corresponding
in a two-phase
acid was
Iron and used
Oxida-
and catalyst oxidized
in
3 and 4 [4171.
in the presence
in substrate
Hydrocarbons
i4161.
of oxidation
at positions
acid by H202
and Fe
The best
were observed:
the extent
to that
No
zeolites
of alkanes
with
The
as catalysts
large pore
of shape
order
[418].
tested
p -0x0 dimer
inside
be
in the presence
hydroperoxide.
oxidized
respect
first
oxidant
14141.
mechanisms
[4151. Cobalt
were
for the oxidation
of n-octane
with
tion of crotonic
group
[4211. The
of phenylacetic
studied.
acid
The reaction
and first
order
was
in Ru and
[422].
Oxidation the presence
of Pd(OAcj2
tivity.
From
ethene
formed,
higher
products
was observed
of cyclohexene
was preferentially
and
could
of N-dodecyl-3,4_dihydroxybenzamide.
was an iron tetraataporphirin
is this
oxide
The results
investigated
and tetraazaporphines
phthalocyanine
cis-stilbene
oxidative
by ~202 was
during oxidants
in the presence
to trans-stilbene.
of the catalyst
phthalocyanines
regenerated
by different
hydroperoxide)
two parallel
of anisole
of the Fe(II1)
is in part
to benzaldehyde,
conditions
by assuming
hydroxylation
H202
of cis-stilbene
yields
mainly
olefins
[4231. Methylbenzenes
to quinones
with
aqueous
glycol
ethylene
yield
H202
HI04
glycol
in AcOH
acetates
glycol
solution
with
diacetate
monoacetates
selec-
is being
as principal
and methylnaphthalenes in AcOH
high
and in
in the presence
were
oxidized
of a Pd(II)-
475 sulfonated
polystyrene
1,4-napthoquinones ities were
rather
tion and reused The Cu(I1) in refluxing
(184)-(186)
ucts
[426].
could
2+ S208 oxidation
or Cu(I1)
and the dimeric
oxidation
salts
An allylic
to
selectiv-
be recovered
of 9-methylanthracene
and aqueous
MeCN.
Side-chain
compound
(187) were
by filtra-
gave
radical
of butenes
with
prod-
the main
prod-
tBu peroxyacetate
3-acetoxybut-1-ene
and a Cu(II1)
[427]. Polynuclear
was studied
oxidation
186
185
Allylic
Selectivities
[424, 4251.
184
mediates
at ZO-80°C.
50 to 70% but 1,4-benzoquinone
low. The catalyst
MeCN/AcOH
ucts
type resin
were
and trans-acetoxybut-2-ene.
complex
aromatic
and Cu(I)
were
supposed
hydrocarbons
were
as interoxidized
by
'- with catalytic amounts of Ce(IV) and Ag+ in a two-phase '2'8 system using (BU~N)(HSO~) as phase-transfer catalyst. Naphthalene could way
be transformed
with
70% yield
in this
[428].
See also
c)
into o-naphthoquinone
[308, 332,
-oxidation
Asymmetric
440, 469, 5081.
of Olefins
epoxidation
of ally1
alcohol
using
tBu00H/Ti(OPri)4/diisopropyltartrate
system
into a practically
The strategy
References
p. 5 I4
useful
procedure.
the
has now been developed employed
consists
in the -in situ derivation its decomposition
of the very
alcohols
could
only
employing
catalytic
ester
tBuOOH
amounts
(6-13 mole
present
pyl tartarate and at least
(5-10 mole
%j if 3A or 4A molecular
with
alcohol
giving
(188) was
both enantiomers
88% optical
yield
were
to asymmetric
i+)- or
:-)-diisopro75-77X
chemical
-
189
epoxidation
of Ti(OPrij4
propyloxiranemethanol [432]. A practical
izeolites)
(189j with
188
Asymmetric
out with
14311.
OH
presence
of allylic
carried
subjected
of
thus pre-
%) and tartrate
sieves
and Ti(OPr i\,4, using
tBuOOH
epoxide
epoxidation
be successfully
of Ti(OPri)4
!4301. Allylic
epoxidation
reactive
14291. Asymmetric
venting
of E-2-hexen-l-01
and diethyl-
2R,3R
in 80% yield
and 96,8%
and efficient
method
with
tBuOOH
-tartrate
gave
in the
!2S,3S)-3-
enantiomeric
purity
for the preparation
of both
enantiomers
of the erythro-epoxy secondary alcohol (191) from the allylic alcohol (190), based on the Sharpless kinetic reso-
racemic lution
process
epoxidation tartrate. into
has been developed.
of
(190) with
The unreacted
tBuOOH,
First,
Ti(OPri)4,
enantiomer
(191b) by epoxidation
with
(191a) was prepared
of
tBuOOH
and
!+j-diisopropyl-
(190) was then and VO(acac)2
transformed 14331.
SW3 nBu
MQ
/ + OH 190
nB”aMe
nB”q_ AH 191 a
by
OH 191 b
477
Asymmetric oxidation of methyl p-tolyl sulfide to the corresponding sulfoxide by tBuOOH in the presence of Ti(OPri)4, diethyl tartrate, and water and asymmetric oxidation of (E)-geraniol (192) with the classical Sharpless reagent was investigated using (+)-diethyl tartrate of varying enantiomeric purity. It was found that the correlation between the enantiomeric purity of the chiral auxiliary and the optical yield of the asymmetric synthesis strongly departs from linearity [4341.
r- -
r-OH
192
Asymmetric epoxidation of the divinylcarbinol (193) with tBuOOH and Ti(OPri)4 in the presence of L(+)-diethyl tartrate gave the epoxides (194) or (195) depending on the workup procedure [435]. Epoxidation of (193) according to the above method in the presence of 4A molecular sieve gave the epoxide (194) in 60% yield [436].
n
194
OH
I
193
I
Ho+ I.*
H
References p. 5 14
195
479
Cyclohexene and different methylcyclohexenes were oxidized with PhIO or m-MeC6H410 in the presence of VO(acac)2. Epoxides and allylic oxidation products were formed: the results were in accord with a free radical mechanism [440]. The dienes (202; R = Et,CoOMe) were epoxidized by tBuOOH in the presence of VO(acac)2 with high regio- and diastereoselectivity to epoxides (203) [4411. PhCOO
OH
The stepwise epoxidation of COD with tBuOOH in the presence of MO complexes was studied. The second epoxidation was at least five times slower than the first one [4421. Epoxidation of refined soybean oil using Mo02(acac)2 as catalyst [4431 and that of sardine oil using Mo(C0)6 as catalyst [4441, in both cases with cumene hydroperoxide, was studied. Empirical kinetic equations were determined in order to optimize operating variables. Epoxidation of cyclohexene by tBuOOH catalyzed by MO complexes was investigated by IR and UV spectroscopy. The results suggested on initial rapid reaction of the catalyst with tBuOOH to give a MO peroxo complex which then epoxidized the alkene [4451. Molybdenum peroxide immobilized on a chelating polymer was used as catalyst for the epoxidation of olefins with tBuOOH. Isolated product yields ranged between 38-89% and the catalyst could be reused several times, preferably after reactivation by H202 [446]. Simple monoolefins were effectively epoxidized with H202 and a catalytic amount of a quaternary phosphonium or ammonium pertungstate at 40-SOOC. The catalyst could be prepared also -in situ by the addition of tungstic acid and Ph3PCH2Ph+C1- to 30% H202 14471. The scope of the tungstic acid catalyzed epoxidation of olefinic alcohols by H202 has been examined. Epoxidation occurred with complete retention of configuration for both eis and trans alkenes and no isomerisation or cleavage of the olefinic bond was observed 14481. This epoxidation afforded in the case of allylic alcohols the same diastereoisomer as the VO(acac)2 + tBuOOH system. Epoxidation of homoallylic alcohols appeared to be much less stereoselective [4491. The transition metal substituted heteropolytungstates (Bu~N)~[H(M)PW~~O~~~ (M = Mn, Co) are remarkably effective
References p. 5 14
480 catalysts oxygen
for the epoxidation Product
donors.
stabilities favorably
of olefins
selectivities
using
! 3,YO%),
PhlO or C6F510 reaction
rates,
as and
(10000 eyuiv, of C F IO per equiv. of catalyst: compare 6 5 with those for metalloporphyrins and related systems
14501. The kinetics has been is the
formation
either
reacts
reaction
these
terminal !4521.
of
olefins
was
species
[453!.
complex
attributed
used
which
NaOCl
in a two-phase was necessary
NaOCl
Ph groups
of
changed
had a synergistic
effect.
:a bywroduct
a H atom onto
the mechanism synthesized
for the epoxidation system.
of
system
Methanol
(204j was
(CH2C12 + H20)
.4511.
in the presence
transfers
changes
+
in a biphasic
to phenylacetaldehyde
and thereby
agent
and KHS05
with
!
for the epoxidation
was investigated.
The new porphyrin as a catalyst
in an equilibrium
on the ueriphcral
as catalysts
and styrene
of styrenej
limiting step -t which
j (TPP)Mn=O'
1 (TPPjMn-O-MniTPP:
LiOCl
of alkenes
as catalyst
of the reaction
latter
manganese
NaOCl,
and Mn'TPP'OAc
the rate
comnlex
complexes
suitable
with
by NaOCl
that
or is transformed dimer
!TPP)Mn!III)
compounds
the epoxidation
tion
the olefin
Epoxidation
kinetics
epoxidation be shown
of the oxomanganese
with
MniTPP-Me-&OAc
This
It could
into the unreactive
Substitution makes
of olefin
studied.
the
of
an 0x0
of the reacand its Mn!III
of olefins
with
No phase-transfer
14543.
204
The Mn(II1) be effective benzene.
complexes
catalysts
[Mncsubstituted
for the epoxidation
Electron-withdrawing
groups
salenjl+
were
of olefins
enhanced
found
with
the activity
to
iodosylof the
481 catalyst; the relative reactivity of olefins depended only slightly on the structure of the substrate. Epoxidation was stereospecific and only minor competition from allylic oxidation was observed [455]. The Mn(II1) complexes Mn(L)Cl, Mn(L')Cl and Mn(L)(N8) (H2L = 205a, H2L' = 205b) have been found to catalyze the epoxidation of alkenes with PhIO. These new catalysts show high chemoselectivity: cyclohexene oxide was the only product in the oxidation of cyclohexene [456].
205a
R=H
205 b
R =Cl
Epoxidation of cyclohexene with PhIO was investigated under identical conditions using different metalloporphyrins
(PMX) as
catalysts. Using TPP complexes,Mn and Fe were found to be the most selective metals (M), with Fe as metal meso-tetramesitylporphyrin was the best porphyrin ligand (P) and among (TPP)FeX catalysts C104 was most effective as axial ligand (X) [4571. Six different alkenes were epoxidized with E-cyano-N,N-dimethylaniline
using
(TPP)FeCl, (TDCPP)FeCl, or (TDMPP)FeCl as catalyst. Best yields (80-100%) were obtained with (TDMPP)FeCl. The rate determining step of the catalytic reaction was the transfer of oxygen from the oxidant onto the iron complex [458]. Along with the epoxidation of alkanes with PhIO catalyzed by Fe tetraarylporphyrin chloride complexes, three important side reactions were observed: formation of PhI02, destruction of the porphyrin ring, and N-alkylation of the porphyrin ligand. The latter reaction was only observed in the case of monosubstituted olefins not hindered in the vicinity of the double bond. The same alkenes act as suicide substrates of cytochrome P 450 [459]. Using Fe(TDCPP)Cl as catalyst for the epoxidation of olefins with C6F510 it was observed that N-alkylation of the porphyrine ligand takes place. Depending on olefin structure 100 to 10000 moles of epoxide were formed per mole of N-alkylated catalyst. This side reaction significantly decreased the act.ivity
References p. 5 14
482 of the catalyst Oxidation
but did not lead to complete
of 2,4,6-tri-tert-butylphenol
-butylphenol
radical
and epoxidation
no-N,N-dimethylaniline catalyst
has been
the formation species
[461].
roperoxybenzoic which
reacts
tuted
styrenes
0 +. copy
acid
with
systems tected
were
developed
than
TPP
The ratio
different catalyst
of exo-
substituted
electron
radical
give a carbocation sylxylene
skeletal (207a)
206,
by C6F510
and
two-phase
Ar=
by UV spectros(CH2C12/H20)
of olefins.
The pro-
stable
and active
!Fe=O)+
!4641.
product
obtained
followed
Epoxidation
as catalyst
formed
from the and using
complexes
as
that the mecha-
to the iron(W)
by radical
collapse
of cis-cyclooctene gave the cis-epoxide
also took place
!465;.
suggest
from the alkene
If trans-cyclooctene
(207b) were
j 3‘
9
or iodosylxylene
The results
transfer
cation
rearrangement
nism was proposed
suecies
the Hammett
[ (tetraarylporphinato)Fe(III)l
and Fe(TPP)Cl
exclusively.
with
to give more
to endo-epoxy
of norbornene
involves
be
!463].
has been determined.
porphyrin
cally
found
radical
was observed
for the epoxidation
(206) were
could
with m-chlo-
In the case of substi-
correlates
+ NaOCl
Ar
epoxidation
porphyrin
to
radical
or Fe(TMP)OH
an oxo-Fe(IV)
Iron(IIL)-porphyrin
leading
Ti: -cation
to give epoxides.
of an intermediate
Ar
nism
of Fe(TMP)Cl
by Q-cyaas
(TDCPP!FeCl
for the oxidations
the rate of reaction
porphyrins
catalyst
gives
olefins
[460?.
olefins
of
and equilibria
porphyrin
rate constants
The formation [462].
Rates
of the iron(oxo
Oxidation
of different
in the presence
investigated.
and minimal
determined
N-oxide
deactivation
to the 2,4,6-tri-tert-
with
to iode
practi-
was epoxidized
in this way
and the carbonyl
compounds
as byproducts.
A carbocationic
mecha-
OH0
- c&J +
Lz
207 a
of cholestery ,1 acetate
Epoxidation systems
as Mo(C0)6
reoselective showed
high
concluded radical
while
+ tBuOOH a radical
that epoxidation process
[466].
(LH~ = 208) catalyzes though
with
low yields
by nonradica 1 reagent
or Fe(C104)3 reagent
with
the
+ H202 was highly
system
Based
p -stereoselectivity.
207 b
like Fe(acac)3
on this
(TPP)FeCl
+ ~EuCOH
observation
+ PhIO
The binuclear
iron complex
the epoxidation
of olefins
(l-3%)
a -ste-
it was
system
is a
(Me4N)[Fe2L(Opc)21 with
H202,
al-
[467].
,CH2COOH
208
The synthetic and their of cis-stilbene (209b-d)
Fe(II1)
analogues complexes
and trans-stilbene was highly were used
iron complex
(209) of bleomycin used
with
suppressed
suggesting
in these
cases
as catalysts H202.
been prepared
for the epoxidation
The epoxidation
of trans-
if the tBu-substituted a highly
derivatives
crow&ad environment
of the
[468].
R'
R2
aH
H
H
bH
Bu
R
209
Referencesp. 514
have
c OMe
Bu
d Cl
Bu
t t t
OBllt OBu OBu
t t
484 The Ru(IV) stilbene
0x0 complex
in acetonitrile
be performed
also
as catalyst
[(bpy)2(py)RuOl
solution
in a catalytic
and NaOCl
case,
due to the oxidative
fission
-porphyrin
iOEP)Os(PBu3)Br
complexes
as catalysts PhIO.
Turnover
the case
numbers
around
of cyclohexene
oxidant,
system
and
100 were
agent.
In
are formed
!469:. The Os(III)-
(TPP)OsiPBu3)Br
of cyclohexene
were used
and styrene
obtained.
was cyclohexanone.
can 2+
with benzyl-
of benzaldehyde
of the C=C bond
for the epoxidation
The oxidation
as phase-transfer
amounts
styrene
! (trpy)(py:lRu(OH2)1
in a two-phase
chloride
significant
however,
in high yield. way by using
as oxidant
dimethyltetradecylamonium this
,2+ epoxidizes
with
The byproduct
If tBuOOH
was used
in as
complex
cyclohexanol was the only product 1470;. The Os(VI) dioxo 2+ reacts with PPh3 to form OPPh3 and the 0s:III) [Os(LH2)02]
complex
Os(L)(PPh3)Cl
the epoxidation mediate
was observed
Several lysts
during
dinuclear
analogous be
See also
solution.
These
mononuclear achieved
with
Th'is latter PhIO.
epoxidation
copper
for the epoxidation
nitrile
could
(LH2 = 210).
of cyclohexene
of olefins
complexes.
have been tested
with
to be much With
4141.
inter-
as cata-
iodosylbenzene
in aceto-
more
than
complex
in the case of cyclohexene
[410, 413,
catalyzes
colored
[471].
complexes
proved
complex
A highly
effective
(211) 70% yield as substrate
14721.
485
d)
Oxidation
of O-containing
Functional
Di- and trimethylphenols quinones metal were
by H202
metal
polyvanadatotungstate actually
oxidized
and the vanadate by HN03 occurs nedione only
and alkali
were
oxidized
as catalysts.
by [VO(O,),i+
2 routes.
to the corresponding
polyvanadatomolybdate
hydrates
[473]. Oxidation
via
Groups
which
was
formed
of cyclohexanol
One of these,
from H202
to adipic
involving
as intermediate,gives a significant 5+ of V 14741.
or alkali
The phenols
yield
acid
1,2-cyclohexa-
of adipic
acid
in the presence Primary
sponding
and secondary
carbonyl
Na2M004. 2H20 as catalyst Oxidation
alcohols
compounds
of furfural,
with
under
could
dilute
be oxidized
H202 using
phase-transfer
thymine,
to the corre-
Na2W04.2H20
conditions
and EtOH by H202 was
or
[4751.
studied
with
MO or W compounds with
as catalysts [4761. Aqueous H202 in conjunction 23amounts of W04 and PO4 , under acidic conditions,
catalytic
provides
a synthetically
tive cleavage
use of tungstate yields
alone
alcohols
olefinic
alcohols
Phenol
Detailed tions
oxidized
oxida-
acids.
decrease
The
of the
was oxidized
by aqueous
ions to yield
investigations
were
between
1.5:1
catalytic
oxidation
than that
of Fe3+
(EDTA)Fe(III)
radical,
the peracid
[4811.
References D. 5 I4
of differ-
and hydroquinone. 3+ Fe . Optimized condi-
with
14791.
The efficiency
by H202
in aqueous
transfer
(212) were
in methanol
and a peroxidic identified
of Fe2'
in the
solution
is higher
from percarboxylic
for the reactive
formaldehyde and
in the presence
catechol
investigated
reagent
[478].
of 84% and catechol:hydroquinone
of phenol
has been
too
ratio of
yields
[4801. Oxygen
(212) as a trapping Phenoxyl
- 2:l
H202
(molar
for the oxidation
alcohols
performed
in good yields
with Mn(OAc)2
was suitable
and of secondary
metal
to aldehydes
in combination
gave dihydroxybenzene
ratios
for the selective to carboxylic
to a significant
The new method
ent transition
from
were
lead tetraacetate
1 : 0.1-0.5).
to
leads
procedure 1,2-diols
[477].
Primary using
useful
of water-soluble
solvent,
iron-oxo
intermediate.
component
as organic
acids using
formed
products
486
CH3 212
:I
CH3 4
CH3
6H
Oxidation catalyzed
of benzoin
by
to benzil
ing peptides
or bulky
of this reaction
thiolates
is shown
by E-benzoquinone
complexes
!Fe4S4(SR)412-
containing
as RS groups.
below
could
be
cysteine-contain-
The catalytic
cycle
14821:
Ph-C -C -Ph d
8
Ph-Cl-i-C-Ph bti
Sodium conversion
bromate
of alcohols
Ce or Ru compounds nary ammonium reaction.
into carbonyl
oxidation
of primary alcohols
of lactic
The effect
oxidized
Ru(PPh3)3C12
and lactic
acid
by N-methylmorpholine
were determined
acid,
and qlycolic
RCHO + H20
to carboxylic G===
[( 7j6-E-cymene)20s2(CI -OH)31(PF6).
for the
in the presence
has been
studied.
of a 1:l
[484 1. Secondary
alcohols
in the presence
in 80% yield
acid by IO, catalyzed
the
of the Ru(III!-catalyzed
N-oxide
for the oxidation
of aldehydes
ing the equation
was selective
of
Quater-
accelerated
by the formation
in DMF to give ketones
stans
Oxidation
was explained
Ru(II1)
reaction.
into aldehydes
14831. The kinetics
for the
in the presence
catalysts
oxidation
alcohols
oxidant
two-phase
acid by peroxodiphosphate
of Ru(II1)
between
compounds
as phase-transfer
The cerium-catalyzed
of secondary
were
found to be an effective
in an organic-water
salts
transformation
complex
was
II
1485'.
of mandelic by RufIII) acids
with
acid,
lactic
chloride water
RCOOH + H2 is catalyzed Raising
of
Rate con-
the temperature
14861.
accordby to 60°C
487 and adding
a base
(Na2C03)
turnover
numbers
glycolic
acid and lactic
is first order could
the rate of the reaction;
be oxidized
with
achieved
[487].
acid by chloramine-T
in oxidant
(214) in 73% yield. necessary
enhances
of up to 100 were
[488].
NaI04
The furan
and 0s04
Isolation
catalyzed
of
by Os(VII
ring of khellin
(213)
in THF to give the aldehyde
of the intermediate
diol was not
[489]. OMe
OMe
0
214
213
Hydroxylation
of the cis-enoate
(216) in 87% yield.
the tetrabenzoate in the presence
0
OMe
6Me
diol
Oxidation
After
(217) the furan of Ru02 to give
owMe
(215) with
transforming ring could
(218)
Os04
afforded
this compound be degraded
the
into by NaI04
[4901.
o*ph
_
216
215
R = PhCOO Me0
Me0
Palladium ary alcohols presence
salts
of K2C03.
References p. 5 I4
catalyze
into esters
the oxidation
and ketones,
Allylic
alcohols
of primary
respectively,
give addition
and second-
by Ccl4 products
in the with
488
halohydrin
structures which,
corresponding hols were chored
at higher
successfully
PdC12
as oxidant useful
ketones
or homogeneous
of K2C03. of
using
as catalyst The method
alco-
polymer-an-
and bromobenzene
was especially into fi4,6 -dien-3-
(219’
A 5-sterols
into the
'491:. Steroidal
into ketones
Pd(PPh3)4
in the presence
(220)
are transformed
temperatures
transformed
for the conversion
-ones
however,
14921.
HO 220
219 A first-order of formic See also
e)
acid
The PhNHNH2
of amines
of indigo
dyes,
catalyzed
murexide,
by EPR spectroscopy
by H202/TiC13
by VO(acac)2 for example
was
PhNMe2
applied
during
14941.
Oxidation
studied.
Oxidative
gave
PhNHMe
polymer-supported
and azo-
o-dianisidine mechanism
were proposed catalysts
by
oxidized
Tc(VI1)
was proposed
14971. prepared
for this
from
or Na noly!D-glutamate) of L-DOPA
H202 or p-benzoquinone _
in acid media
by
or poly-
by H202
CH2=CH(CH2)3CH=CHCH2NEt2 14991.
into MeCO(CH2)3CH=CHCH2NEt2 by
and lumogallion
oxidation
amine
of
The oxidation
of ethylenediamine
and Na poly!L-glutamate)
tertiary
complexes
!496!.
lumomagneson,
complexes
for the stereoselective
selectively
H202 using
was studied
carmin,
Mechanisms
The unsaturated
of Na2PdC14
dyes with
with Mn(I1)
as catalysts.
[Re!tetpy)!OH)21+
was
Compounds
was observed
of different
The chiral
[498:.
Organic
triethylenetetramine
H202 was studied
were
!4931.
[495].
with
amines
for the oxidation
5781.
was observed:
Oxidation Mn(I1)
radical
by Cu(I1)
of phenylhydrazine
by PhIO2
dealkylation
573,
of N-containing
the oxidation
was determined
by S208*- catalyzed
[461, 569,
Oxidation
benzene
rate constant
is catalyzed
reaction
[5001.
in the uresence
The oxidation
of
by Cu!IT).
A
489
See also
f)
L419, 459,
Oxidation
of P- or S- Containing
The asymmetric sulfoxides
416, 5971.
oxidation
was achieved
of catalytic complexes
amounts
(221,222).
Organic
of sulfides
with
cumene
of optically Optical
into the corresponding
hydroperoxide
active
yields
Compounds
Schiff
ranged
in the presence base-oxovanadium@V)
between
20-40%
[5011.
R
O,i,O / - ’
OO/\ \;,
c&t,
-
_N/
&“&
lN-
y,? 221; R= H,OMe,OEt, It was Mo(IV)
transfer
that
the Mo(V1)
[224] reduces
in DMF
sulfoxides, ferase"
shown
complex
222;
tBu
solution.
N-oxides
system
complex
several
Thiols
and Ph3As0
R = H,Me
(223) oxidizes
organic
compounds
and PPh3 were oxidized were
reduced
by this
while
"0x0 trans-
[502].
+
Accordingly,
complexes
(223) and
of sulfoxides
R2SO+
Asymmetric
2
R’SH
oxidation
by thiols
and diethyltartrate high
as catalysts
+
R’SSR’
+
H20
(225; n = 2) with
gave the corresponding
and optical
for
[503]:
of dithiolanes
(226) with
chemical
(224) acted
RSR
-
Ti(OPri)4,
ReferencesD. 5 14
x0
224
223
the reduction
and the
by oxygen
yields.
tBuOOH,
sulfoxides
By contrast,
the
490
analogous
(225; n = 3) gave much
dithianes
lower
optical
yields
15041. 0 II
R\C,sl(CH2)n
R’/
R\C,sl
-
\S/
R’/
225
Asymmetric been
furnished
(227a) and
226
S-oxidation
investigated
system
using
of the chiral
different
predominantly
(227bj,
the trans
the two stereoisomers
from
N-R’
x Rs
R2
oxidants.
isomer
(227d)
227
from
type
of
(229) was
studied
Ti(OPri)4.
(228) with
The relative
on the Ti compound
in the case of
(227~) and a mixture
R2
R3
a
CH20H
CH2Ph
Me
Me
b
CH20H
CH2Ph
nPr
H
c
CXSle
MO
tBu
H
CR2Ph
Me
Me
active
hydroperoxides
and in the presence
of the cis and trans
composition
of these
strongly
HW,
NR’
-
R”R”
228 (racemic)
229
6 230 (four
of
depended
R
+ r-i X
of
of
isomers
[506].
S
of
R'
in the absence
(230) and the enantiomeric
The tBuOOI_I+ Ti(OPr')4
R
optically
yields
(227) has
[505].
dCKNe
Oxidation
thiazolidines
the cis sulfoxide
R d S
(CH2)n
\c/
enantiomers)
491
Thiophenol aniline
was oxidized
N-oxide
Optically
active
tion of chiral as catalyst.
to diphenyldisulfide
in the presence triols
of Fe(TPP)Cl
(232) could
allylic
be prepared
J3-hydroxysulfoxides
The diastereoselectivity
between
72-95%;
sulfone
it dropped
if the sulfoxide
J5071.
by the hydroxyla-
(231) by Me3N0
of the reaction
was previously
to 308, however
by N,N-dimethyl-
as catalyst
and 0~04
ranged
oxidized
to the
[508].
Me OH 232 Thioethers -transfer
were
catalysis
and Cu(OAc)2 See also
6.
Metal
Oxidation
were
by chromic electron
acid.
-5OOC
studied.
The data
atom abstraction
References p. 5 I4
releasing
substituents
that
the initial
favored
pathway
to
was extremely
toluenes
fluorochromate step involves
of eudesmol
an
J5llJ.
upon mixing
of substituted
by pyridinium
rate cinnamic
hydrocarbons
The reaction
is
to form
metallo-
Second-order
in Ccl4 was oxidized
[513J. Oxidation
bond
of substituted
oxidized
hydro-
hydrogen
reactions
a radical
and ketones.
of oxidation
aldehydes suggest
J5101.
substituents
of n-hexane
The kinetics
the corresponding
latter
Cr02(00CCF3)2,
alcohols
model
step allylic
for the oxidation
withdrawing
a solution
Hiqh Valent
to the double
In these
Electron
trifluoroacetate,
J5121.
then adds
as intermediates
determined
give predominantly rapid:
phase-
Groups
in the gas phase
In the first
products.
can be supposed
constants
ionic,
alkenes
processes.
and other
Compounds - -.-__~-_with
or Hydrocarbon
to form CrOH which
aldehydes
Chromyl
of Orqanic
of CrO+ with
oxidation
abstracted
acids
under
of Bu3(hexadecyl)P+
Complexes
of Hydrocarbons
Reactions
cycles
by NaI04
in the presence
[434, 6141.
StoichiometricOxidation
carbon
into sulfoxides
[5091.
Transition a)
oxidized conditions
(233) with
at to
has been hydrogen dipyridyl-
492
chromium
trioxide
gave
(234) and two isomeric
Me
ketones
Me
cn
CMe 20H
I t!j
[5141.
CMe20H
Me 233
Alkynes compounds
were
by
The role with
234
oxidized
of mercuric
the alkyne
in the presence
acetate
thus
Cc -dicarbonyl
to the corresponding
(HMPA)MoO(02)2
is probably
favoring
of mercuric
to form a
oxidative
attack
acetate.
Tt -complex
by the metalperoxi-
de 15151. The kinetics
of permanqanate
Cr,p -unsaturated buffered
carboxylate
to electronic These
important.
effects
results
to which
the MnOi
to yield
a metallacyclooxetane
tion
of solid
C=C bond
acid
to yield
THF solution. creased
ion undergoes
paraffin
the carboxylic
tadiene
with
KMn04
salts
of reaction
alkenes Mn02.
in CH2C12
This product
phonium polar
ions had
solution
is accompanied
derivatives
solvents
little
effect
has been
de-
by MnOq
in ben-
of dicyclopen-
It was shown
intermediate.
at the
in a dilute
substituents
Oxidation
cation
improved
cleaved
of quaternary
that
the rate
by the rate of decomposition
detectable
permanqanates
In the oxida-
in the presence
investigated.
is stabilized
of styrene
organic
15191.
the C=C bond
with KMn04
of ethylbenzene
size of the ammonium
by Bu3MeN'Mn0i
Oxidation
products
were
to be
according
of n-hexadecane
and bulky
Oxidation
was determined
increasing
main
by Bu4NOH
has been
spectrophotometrically with
as
with 15161.
[5171. Olefins
increased
[518].
zoic acid was catalyzed
ammonium
addition
appeared
mechanism
cycloaddition
by KMn04,
Conjugation
the yield
the accepted
in phosphate
to be not very
factors
intermediate
selectivity
aldehydes
found
but steric
support
of substituted
investigated
(pH 6.8). The rate was
solutions
sensitive
ion oxidation
ions were
of a
The rate
increased
!5201. Oxidation
by the
formation
by adsorption
of the alkane
by quaternary
ammonium
studied
such as acetone on the rates
in different the structures
of reaction:
of
of colloidal [521j.
and phos-
solvents.
In
of the cat-
significant
dif-
493
ferences
were
as CH2Cl2 (235) with
however,
in less polar
[522]. Oxidation
cetyltrimethylammonium
6 -1actones oxidative
found,
or toluene
(236) with cyclization
R
good yield.
organic
permanqanate One carbon
solvents
such
6 -hydroxyolefins
of y- and
leads atom
to y - and
is lost in this
[5231.
OH
‘C’ R,/ \
236 (CH~),,CH =CH2
235
The ethylenic
lactones
the dibenzobutanolides cyclic tate)
compounds
(237, R1-R6
(239)
(238) and
15251 were
= H,MeO,OCH20) oxidized
(240) by Ru(IV)
tetrakis(trifluoroace-
in situ from Ru02, trifluoroacetic -tris(trifluoroacetate), and BF30Et2 in CH2C12-
formed
acid,
R’ 238
References
P. 5 14
[5241 and
into the tetra-
Tl(II1)
494
OMe
OMQ
R =H,Ot'&
OMe
OMQ
240
239
Transformation was
investigated
nes,
of allylic
using
and acetates
opposite
perbenzoic
acid
osmylation
i526].
used
achieved
Optical
Hydroxylation
of olefins
to vicinal
in the nresence
up to 86% were
achieved
from L-tartaric
for this purpose.
Optical
yields
with
siloxa-
diols
by 0~04
of chiral
with diamine
acid
(241)
have also been
up to 90% were
(242) in the case of trans-stilbene
/a
sulfides,
in epoxidation
derived
example
by 0~04
with m-chloro a hyperconjuqative model for
enantioselectively yields
diols
diastereoselectiv-
diamines
15271.
Chiral
sulfones,
The observed
and did not support
be performed
diamines.
to those
into vicinal
silanes,
as substrates.
ities were
could
chiral
groups
achieved
for
15281.
NM42
242
241
NMe2
The indenopyrene by first sulting
treating diol with
(243) was transformed
it with
0s04
activated
into the quinone
in py and then
Mn02
oxidizing
!529]. 0
243
244
(244)
the re-
495
Oxidation
of E-xylene
the effect
4_Methylbenzaldehyde, acetate
were
probably
nium
selectivity
by bromine
and Co(II1)
reaction
transfer
is the
H atom abstraction
dation
of olefins
glycol
monoacetates. were
her.
found
intermediate
were
[533].
acidic
Several
intermediates
nism
involving
for this
15351.
one
with
solution
were
were oxidized
monoacetates
media an
organic
as
with
solvents and ver-
to acetaldehyde The nitrito the reaction
by spectros-
by PdC1(N02)(MeCN)2 ref.
was
radical
-pinene
during
identified
(AS 1985,
intermediate
and was high-
verbenol
studied.
complex
in
515). A mecha-
(245) was now proposed
[536].
245
References p. 5 I4
a
of ethene
was
allylic
involving
of
products
and
[5321.
a cation
and in different
of the process
the acetoxonium
olefins of tri-
in acidic
oxidation
into a nitrosyl
Olefins
[5311. Oxiacetates
olefins
mechanisms:
Oxidation
operate
system
monoacetates
complexes
oxidation
[534].
to glycol
reaction
plausible
gave allylic
and an other
ammo-
The regio-
in the Co-containing
from aromatic
solutions
Side-chain
that the two oxidants
of glycol
by Pd(I1)
in CH3C1
was transformed
solution
formed
The allylic
complex
AcOH
the yield
is
by Ce(IV)
in the oxidation
The liquid-phase
predominant
methods
in AcOH
by two different
by Pd(ONO)C1(MeCN)2
copic
[5301.
in the Ce-containing
to be more
products,
were
investigated.
benone
Brz
In the case of disubstituted
intermediate
in aqueous
PdC12 was
The reaction
investigated.
step while
seems
of xylenes
to proceed
organometallic
first
olefins
Both products Oxidation
suggests
by CO(OAC)~
the main
tetrasubstituted
has been
and
studied.
and 4-methylbenzyl
radicals
mechanisms:
system
acetates
alcohol products.
anion
acetate
of the reactions
different
electron
oxidation
has been
of 5-substituted-1,2,3_trimethylbenzenes
nitrate
with
acid by Co(III)-acetate
reaction
4-methylbenzyl
the organic
initiated
oxidation
in acetic
of Br2 and py on this
Oxidation aldehydes
of toluene
by
be catalyzed
by anionic
rate enhancements interaction See also b)
were
into the correspondinq
in a two-phase
reaction
surfactants like Me(CH2)llOS03Na. interpreted
in terms
The observed
of a micelle-substrate
of Olefins
The polymeric
yield
peroxo
titanium
found
derivatives
to epoxidize
Ti02tL: :HMPA:.H20
tetramethylethylene
with
15381. COOH
COOH
I
yN HOOC /U‘N
HOOC
‘I J3‘N
246 The novel red and used
247
vanadium(V)
alkylperoxy
for stoichiometric
showed
that
in agreement
with
process
step.
complexes
epoxidation
the olefin
the rate-determining
dation
benzcould
[334, 5641.
(L = 246 or 247) were
studies
system
:537 1.
Epoxidation
5-15%
derivatives
(NH4)2CeiN03)6
coordinates
The features
the general
(248) were prepa-
of olefins. to the metal
of these
characteristics
Kinetic prior
epoxidations
of the Halcon
to are
epoxi-
[539]. R
/ b -
248
0’
R =H,Me,CI,NO2
\ /
Epoxidation occured
of cis-2-butene-1
stereospecifically
4-diones
(249) by Mo05.H20.HMPA
to give the cis-epoxides
(250)[540!. R=Ph,Me,OMe
0
PhC
R
t
6
0
___c
ph-C
A 8
249
-R d
250
497
Stoichiometric (M = W,Mo) tungsten
complexes
complex
two peroxo geraniol
has been
was more
groups
react
gave
studied
in CH2C12
rates
(252) with
the epoxides
suggests
OH
at 40°C.
The
be shown that
the
[5411. Epoxidation
the same complexes
(253) and
does not involve
with M0(02)2(HMPA)
and it could
at different
in regioselectivity
and W complexes
of olefins
active
(251) and linalool
chloroethane change
epoxidation
(254), respectively.
that epoxidation
a coordinated
-
with
substrate
of
in diThis
these MO [5421.
OH
253
251
OH
OH
G\
0 252
254
Peroxomolybdenum ligands
were
found
complexes
to exhibit
(255, 256) containing
asymmetric
induction
chiral
in the epoxida-
tion of -trans-2-octene. Optical yields were about the same (highest value 11%) whether monodentate or bidentate chiral ligands were used
[543].
255,
L* = e.g.
256;
L* =
L” H20
O,i,O hyyd L* See also
References
p. 5 14
[526].
Q_CJ.
?” 40
CH3 CHC ‘NMQ2
498
Oxidation
Cl
of O-containing
Oxidation
of benzaldehyde
in HClO 4 was
V5'
first
order
indicated
found
by vanadium(V)
The kinetics
of oxidation
The kinetics acid media mic
acid
was
of butene-1,4-
dation
ied using groups
of oxidation
investigated
with
in the presence complex
acid and tartaric
in ayue-
in strong
oxidation
by chro-
of lactic
acid.
[5481. Oxi-
(tBuOj2Cr02
was stud-
[549]. The two secondary
be oxidized
selectively
Cr(V1)
was suggested
acid with
methods
(257) could
(Cr03 in aq. H2S04)
PhCONy
of glycerol
considerably
IR spectroscopic
of taxol
and pentane-1,5-diol
were
[547]. The rate of iPrOH
of a termolecular
of oxalic
anion
alcohols
i5451.
i546].
studied
increased
The formation
and less than
of 20 heterocyclic
AcOH were measured
by the 12-tungstatocobaltate(II1) acid
in oxidant
by
and spectrophotometric results 5+ of a complex between V and hydrated benz-
in aqueous
ous perchloric
order
derivatives
Kinetic
The rate of oxidation
[5441.
Groups
and its substituted
to be first
in substrate.
the formation
aldehyde
Functional
with
to yield
Jones's
compound
OH
reagent
(258)
15501.
0 .O--
PhA
0
&i
OCOPh 257
258
In the presence complex
chromate
in CH2C12
solution
or ketones.
of quaternary
salts which
Oxidation
was even more
species
reaction
was performed
fixed this
onto form
nicotinic dichromate
were
catalytic pyridinium [551].
be used
for the conversion
ammonium
-transfer
ammonium
could
applied with
conditions.
efficient
Two new mild,
acid and isonicotinic
complex
ammonium
Cr(V1)
dichromate
quaternary
amounts
and the phase-
chromates could resins
also be
and used
reagents
developed.
were
gave oxidants
into aldehydes
solid-liquid
oxidation
acid were
Cr08
if the
catalytic
CrO8 under
These
or quaternary
and isonicotinium
of alcohols
in only
solid
species,
as homogeneous
suitable
in
based
Nicotinium for the
on
499
oxidation quinones with
of alcohols and thiols
into carbonyl
CrO
and different 3 in 60-80% yield. Thiols
nium oxychromate dichromate tion
oxidized
were
and benzylic
in DMF at 25OC
selective
alcohols
to the corresponding
te in CH2C12
into disulfides
Allylic
with
sieve
carbonyl
(259) was dichroma-
[555].
p”Tg”
5% 0
0
OMe
OMe
260
alcohols
derived
from carbohydrates
to the corresponding
reasonable
for the oxida-
(260) by pyridinium
of 3A molecular
259
be oxidized
with pyridiImidazolium
to the corresponding
-
OH
reagent
2-octanone
The deoxyhexapyranoside
ketone
in the presence
[5531.
into
of 2-octanol
salts gave
oxydichromate
[554].
hydroquinones
Oxidation
ammonium
oxidized
found to be a mild
of allylic
compounds
[552].
quaternary
or pyridinium
was
compounds,
into disulfides
(40-80%)
yields
enones
with
(e.g. 261) could
pyridinium
dichromate
[556].
261
The bisphosphonium found
bichromate
to be a selective
benzylic
primary
aliphatic
nose
each
alcohols
alcohols
Oxidation order
were
acid
References
the corresponding
p. 5 I4
to the corresponding
[558]. Oxidation with ketones
was
of allylic aldehydes.
or Saturated
[557].
by pyridinium
and substrate.
like CH2=C=CMeCH2CH(OH)Ph gave
(Ph3PCH2PPh3)2+(Cr207)2V
for the oxidation
not affected
of D-glucose
in oxidant
and formic
agent
fluorochromate
Reaction
products
of allenic
pyridinium in 71-87%
secondary
chlorochromate yield
is first are arabi-
[5591.
alcohols in CH2C12
Tetrasubsti-
500
tuted were
furans
(262)
oxidized
CR = COOMe,
by pyridinium
COMe;
R' = substituted
chlorochromate
to qive
chenyl)
!Z)+kCEF+CR'OAc
[560]. R
R‘ 262
Me
Treatment reagents cyclic
of the tertiary
results
ethers
strongly
cyclooctenol
in transannular
(264) and
depends
(265). The ratio
on the nature
nium chlorochromate,
Na Cr04, 2
(263) with
oxidative
Me
to the bi-
of the two products
of the Cr(VIj etc.j
Cr(V1)
cyclization
reagent
(Cr03, pyridi-
[561].
Me
Me
I’
,’
0 0
0 263
Kinetic
studies
in acid media to alcohol tion first
264
showed,
and second
of phenoxyacetic order
each
ric, tartaric, the presence additives
that order
of Fe(II), videly aldehyde
alcohol
of Cl-C3
the reaction with
acid with
in oxidant
varied
of the ally1
of the oxidation
or adipic
The unsaturated
265
respect
As(II1)
or Sb(III!.
respect
[5621. Oxida-
in aqueous
AcOH
of cit-
The effect
substrata
by the Mn02
15641.
oxidation
[565].
267
in
of these
COOEt
266
is
by Mn0-4 was studied
on the organic
(267) was prepared
(266) in 72% yield
with
k5631. Oxidation
and sugars
and depended
by Mn(II1)
order
to MniIII!
permanganate
and substrate
acids,
alcohols
is first
501
Aldehydes oxidized
hydroxyl
groups
KMnO 4 to the corresponding
with
95-9890 yield reaction
with protected
using
medium
a mixture
of tBuOH
(e.g. 268) were
carboxylic
and aqueous
acids
in
NaH2P04
as
[566]. CHO ._,OCH2Ph
-
268 Oxidation was
shown
terms;
of simple
to follow
aldehydes
a mixed
only one of these
mixture
order
to carboxylic
acids
rate equation
was substrate
by K2Fe04
containing
dependent
of K2Fe04.A1
0 and CuS04. 5H20 efficiently oxidized allyl2 3' and saturated secondary alcohols to the corresponding
ic, benzylic, aldehydes
or ketones.
inactive
Since
for the oxidation
for selective
oxidations
this
solid mixture
of primary
was practically
alcohols
it could
like that of (269) into
(270)
0
OH
OHOH
be used [568].
The kinetics glycol,
of the oxidation
and tetraethylene
RuC13. nH20 posed
anion
involves
oxidizes
Ph3P to Ph3P0. phines depends
two-electron
tartaric,
References P. 5 I4
acid
(formate
transfer
and glycolic
their ligand
slowly which
the
breaks
is then
up oxi-
[(bp~)~Ru(o)(PEt~) 13-
other
acid
and
tertiary
activity [5701.
phos-
strongly
The kinetics
ion) by [Ru(bpy)2(py)(0)12+
suggest
that oxidation
[5711. Oxidation acid
The pro-
between
to propionic
containing
substrates,
The results
hydride
and a Ru hydride
of the phosphine
of formic
studied.
this complex
Ru(IV)-oxo complex
complexes
diethylene
and using
of a complex
propionaldehyde
organic
on the nature
of oxidation has been
lactic,
Analogous
glycol,
has been determined.
species;
products
to acetone,
also oxidize
of ethylene by [Fe(CN)613-
catalyst
[Fe(CN)6i3- [569]. The iPrOH
(95 %)
the formation
and a Ru(II1)
into the intermediate by
glycol
as homogeneous
mechanism
glycol
dized
three
[5671. A solid
by
occurs
of Na salts
[Fe(CN)6]3-
catalyzed
by a of by
502
Ru(VI)
in aqueous
independent
of
no1 by Ce(S04)2 catalysts.
alkaline
was
the catalytic
effect
of butanol
and substrate A svstem
order
decreased
composed
of
oxidized
ted in aqueous
ent
substituted investigated.
(TPP)CoCl
by
studied.
The rate first
transfer step
expression
'5731. Oxi-
order
in oxidant
acid
The kinetics
was derived
catalyzed of lactic
of oxidation
alcohol
investiga-
solutions.
The reac-
of oxidation
of differ.+ [R~L(OA~)~(H~O)~!
by
radical
oxi-
intermediate
for the oxidation
of propano-
15783.
acid and mandelic
proceeded
radical
[575]. Oxida-
by the one-electron
by Ir(III)
acid by Ni
via C-C bond
and CO2 were detected of aliphatic
in oxidant
from
II cation
ions has been
to a semiquinone
The reaction
primary
3+
leavage;
as products
alcohols
has acet-
15791.
by Ni 3+ is both
and substrate; on outer sphere electron 3+ to Ni was proposed as the rate-determi~ning
[580]. The dimeric
has been
Cu(I1)
synthesized.
(stoichiometric complexes
in two,
The oxidation
mechanism
of Ce(IV)
Both
lenes
seemed
were
quinones
the oxidation HC104.
Ce(IV)
was
of catechols steps
dimedone,
studied
by CuiII)
[581]. and
3,5-dimethyl-2-
!582!. The kinetics
of glyoxylic
acid
and
and pentamminegly-
perchlorate
were investigated in acidic sulfate 2and [Ce(S04)3] appeared to be the oxidant speglyoxalate
while
to be the only oxidant
oxidized
by
oxidation
one-electron
oxidation
Ce(S04)2
for coordinated
Ce(S04)2
of 3,5-di-tert-butyl-o-semiquinone of this complex proves that the
of dihydroresorcin, with
oxalatocobalt(II1) media.
complex
The existence
or catalytic)
proceeds
cyclohexene-l-one
cies
[576].
benzaldehyde,
order
by Co(II1)
The rate was determined
[Fe(CN)6]3-
aldehyde,
the
bnt with Ru04
radicals
1,2- and 1,4_dihydroxybenzenes
The oxidation been
and its
to phenoxy
acid and acetic
in AcOH
of the hydroquinone
[577]. A rate ne-2
as
were different:
in Ru-trichloride
found to be first
phenols
sulfuric
faster
was
dation
Ru04
at high concentrations
by 0~04 was
and
cyclohexa-
and
RuCl3.nH2O
of the two reactions
first
of carboxymethylcellulose
tion was
with
in RuiVI)
of 2-methyl
/574].
[(TPP)Co+']C12 tion
was
is first order
1572]. Oxidation
investigated
The kinetics
rate of oxidation
dation
solution
[Fe(CN)6j3-
with
(NH4)2Ce(N03)6 of D-altrose
No evidence
for free glyoxylic [583!.
1,4_Dimethoxynaphtha-
high para
regioselectivity
under
conditions
mild
by Ce(C104)4
for initial
was
complexation
acid
to l,$-naphtho[584]. Kinetics
studied
in aqueous
was obtained
[585].
of
503 See also
d)
1587, 5961.
Oxidation
of N-containing
Oxidation
of H2NCOCOOH
(oxamic
the unprotonated
substrate
substrate
Second-order
[5861.
of various were
Organic
reacted
Compounds
nitroalkanols -supported
[5871. Nitroketones dissolved
Cr03.
Irradiation
of acetylindoles
nes
[5891.
(272)
showed
that
for the cooxidation
and oxalic were produced
in dichloromethane
Oxidation
K2Cr207
than the protonated
rate constants
2,6-diphenylpiperidin-4-01s
determined
by
acid) faster
with
by ultrasound
acid with
Cr(V1)
by oxidation
of
montmorillonite-
improved
the yield
(271) with Mo05.0P(NMe2)3
gave
-
[588J.
indolo-
R= H, Me,Ph
271
The kinetics by Mn(IV) oxidant
of oxidation
have been
and
studied.
substrate;
-determining
step
of aniline Reactions
hydride
[590].
transfer
Stilbazoles
2- and 4- isomers
underwent
the corresponding
pyridinecarboxylic
tive under
act as an autocatalyst MnOi
in phosphate
cies
formed
buffered MnO2
buffered
solutions
with
HPOi-
were
and H,MnOi
1-Phenylsemicarbazide PhN=NCONH2. studied
and activation by
iFe(bpy)3]3+
of the anilinium
References
p. 5 14
ions
of colloidal
and the kinetics
in the oxidation
of
found
to
by
Mn(IV)
spe-
particles
of this
ion to reaction
were
constants
of substituted with
of
[593].
on the rate
The data correlate
[595]. Oxidation
and
was unreac-
amines
by ferricinium
of substituents
was studied.
was
The
PhCHO
in phosphate
to the surface
is oxidized
The effect energies
to consist
ions bound
Mn02
The soluble
by MnOi
in
as the rate-
to yield
of aliphatic
[5921.
anilines both
by KMn04.
the 3-isomer
Colloidal
of amines
The equilibrium
[594].
acid:
[591].
solutions
shown
oxidized
cleavage
in the oxidation
in the oxidation
first order
was proposed
were
oxidative
the same conditions
and substituted
were
anilines
the pK values
benzylalcohol
or benzyl-
by [Fe!CN)613- in presence of Os(VII1) as catalyst is first order both in oxidant and substrate 1596:. The kinetics of the
amine
Ru(III)-catalyzed been first
oxidation
The reaction
determined. order
of triethanolamine
in the substrate
isoquinolinium
cation
idly oxidized
by
are inhibited
second
in oxidant !597'.
related
5991.
= ‘Nh cc
product.
behave
(273)
Other
similarly
=‘N-Me cc
-
I
are rap-
Both oxidations
ion reaction structures
and both
The 2-methyl-
cation
(274), respectively.
by the ferrocyanide with
(FelCNj6j 3- has
to 2-methyl-l-isoquinolinone
!Fe(CN)6j3-
cations
order
and the catalyst
and the 1-methylquinolinium
and 1-methyl-2-quinolinone
eroaromatic
was
by
1
het!598,
273
0
=1 +; 00
*
274
N
tk
l-Azabicycloalkan-2-ones Oxidation
occured
and afforded ylic
like
regioselectively
either
acid derivatives
(275) were
at the bridgehead
the corresponding like
(276)
oxidized
hydroxy
amino
was performed combination
R’CON
acids
oxidized
(277)
(R = Me,Et;
by Ru04 to give
in a two-phase
system;
276
N
R' = Me,Et,Cy,OEt; lactams
EtOAc/H20
(278). Oxidation
was the best
[601].
A
(CH2),,
Y
-
R’CON
A
(CH21n
v tOOR
277
atom
or carbox-
0
TIJ
were
Ru04.
[600].
275
Cyclic
carbon
compounds
HOOC
n = 1,2,3)
with
dOOR 278
solvent
505
Oxidation (280). Under lactams
of cyclic the
amides
(282) and
cyclic
Ru04
gave cyclic
benzylamines
(2831, and benzamides
r(fH2)tl RCON-CH2
(279) with
same conditions
(284)
[602].
F(fH2)” RCON-C=O
-
lactams
(281) gave
R = H,Me,Ph n = 5,6
280
279 r(CH2)n
p2&l
PhCH2N - CH2
-
282 W2)n rr PhCON - CH2
281 n
q
5,6
Kinetic benzoquinone
data
for the oxidation
by the Co(II1)
the rate-determining the semiquinone
tions
buffer
HEPES
Oxidation
Probably
285 of hydroxypyridines was
studied
the alcoholic
with
to
OH is oxidized
the same condi-
Ce perchlorate
to about
equal
Diastereoselective (289) was achieved
in perchlo-
[6051.
of thianthrene-5-oxide
286
References p. 5 I4
of the substrate
(285) and N,N-dimethylethanol-
of P-, S- or Halogen-containing
Oxidation
esters
that
indicated
H
ric acid medium
leads
to
[co(NH~)~C~IC~~
like EtOH do not react under
[604].
Mo,W)
284
of p-H2NC6H4N(Et)CH2CH20H
complex
by Cu(1).
alcohols
Oxidation
e)
283
step was the conversion
used
are oxidized
but simple
PhCON -C =0
16031.
The widely amine
r(yH2)n +
PhCH2N-C=O
amounts
Organic
(286) with of (287) and
287 CL-hydroxylation
Compounds
(HMPA)MO5 (288)
(M = Cr,
[6061.
288 of the chiral
with MoOg.py.HMPA
carboxylic
in the presence
of
KN(SiMe3j2
and
Hydroxylation
K(sec-BuO).
form of the esters no substituents
and was practically U
at the
carbon
proceeded restricted
atom
over
the enolate
to esters
having
i6071.
289
Oxidation Reaction
of thiocaprolactam
products
were
nism of the permanqanate (290, 291j has been the formation diester
by KMnO4 was
identified
!6081.
ion oxidation
studied.
of thienyl
A rate-determining
of a metallacyclooxetane
(293) was proposed
investigated.
The kinetics
and mecha-
propionates
step
leading
(292) or a cyclic
to
Mn!Vj
16091.
x = H,Br,Me Y = H,D,Me R = H,Me,Ph,CN 291
290 I I
I
-c-c-
m&--cl O--n+
A_
\o
d
1 40 0
0
‘Ml-’ 4 \_
293
292 The pertechnate form Tc(Vj-cystine Oxidation in substrate, was
found
aliphatic during
ion oxidizes
oxidant
the reaction
has been
to iron(III)
agent
examined.
Since
lFe(CNj6,1x-
to
is first
ferrate
order
(K2FeO4j
for the transformation
and sulfones.
Iron(VIj
[612]. The kinetics
leucothionines
acids
f6101.
j611j. Potassium
oxidizing
to sulfoxides
in strong
complexes
by alkaline
and alkali
to be a strong sulfides
L-cysteine
and Tc(Vj-cysteine
of methionine
tion of disulfonated Fe3+
0
(parent
the formation
compound
of
was reduced
of the oxidasee 294) by
of the thionine
skele-
507 ton (295) involves flattening of the phenothiazine moiety, the necessary electron transfer is much more difficult if the organic molecule is a ligand within a metal complex than if it is the anion of an ion pair [613].
Complete oxidation of (H~NCH~CH~S)~ to NH3, carbonate and sulfate by ditelluratocuprate(II1)
in aqueous KOH is catalyzed by
0~04 [614]. Cysteine is quantitatively oxidized to cystine by an excess of the Cu(I1) complex of tris[2-(2-pyridyl)ethyllamine [615]. Triphenyl phosphine was oxidized by (BU~NI[PMO~~O~~I to Ph3PO; the molybdophosphate anion was reduced to [BU~NI~~PMO~~O~~I [6161. 2-Bromo-m-xylene could be oxidized to 2-bromoisophthalic acid by Na2Cr207 at 230°C under 20 bar CO2 pressure [617]. Polymer-supported H2Cr04 was applied for the oxidation of E-C~H~(CH~X)~ (X = Br,Cl,H) to E-C~I-I~(CHO)~ [6181. See also [349, 471, 526, 552, 553, 5701.
7.
Electrooxidation and Photooxidation p -Cyclodextrin accelerates the electrocatalytic oxidation of
NADH by ferrocenecarboxylic acid (Fca). Probably a cyclodextrin-Fca+ complex acts as the effective oxidant [619]. Constant-potential electrolysis of a solution of (TMP)FeOH
in the presence of
olefins was found to produce epoxides as major products [6201. A system consisting of Ru04/Ru02 and Cl+/Cl- redox couples has been developed for the indirect electrooxidation of secondary alcohols to ketones, of primary alcohols and aldehydes to carboxylic acids and of diols to lactones and keto acids. Oxidation proceeds in an aqueous-organic two-phase reaction mixture; Ru04 is the actual oxidant of the organic substrate [621]. The oxo-bridged Ru(III)-
References
p. 5 14
508 dimer
the electrooxidation Actual
solutions. situ
was used
i(bpy)2iH20)RuORu(H20)(bpy)2]4+ of alcohols,
oxidant
[622]. A series
qands
were
catalytic benzene
tested
of Ru complexes
for
in basic
qenerated
dimer
in
bpy and phen
containing
transfer
acids
and amino
was the Ru(IV)Ru(Vj
as electron
oxidation
sugars,
as a catalyst
mediators
li-
in the electro-
of 1,2,4,5_tetramethylbenzene
and pentamethyl-
16231.
D-Fructose
was oxidized
ions under
photochemical
formedwere
reoxidized
to D-erythrose
conditions.
Since
by atmospheric
oxidation
of D-fructuse
could
hydroxide
was precipitated
by Fe(III) Fe(I1)
oxygen,
be performed
or Mn(II1)
and Mn(I1)
thus
the photochemical
catalytically.
from the solutions
No metal
!624].
V. Reviews
Homogeneous
catalysis by transition-metal
complexes.
330 refs.
[625]. Catalysis Recent
by zeolite
developments
Industrial
metal
Organometallic
complex
15 refs.
catalysis
of homogeneous
chemistry
Hydroformylation.
compounds.
in homogeneous
applications
Homogeneous
11 refs.
inclusion
catalyst
[627].
catalysis.
design.
and catalysis
[626].
50 refs.
7 refs.
[629].
in industry.
An old yet new industrial
route
[628].
[630].
to alcohols.
16311.
Asymmetric
hydrosilylation
and hydrocarbonylation.
112 refs.
[632]. Homogeneous
mixed-metal
to N-acyl- a-amino Homogeneous
catalytic
new process
for acetic
Convert Direct
methanol route
from
catalyst
acids
systems:
new and effective
via carbonylations.
reaction
of CO, H2 and methyl
anhydridelvinyl
to ethanol synthesis
21 refs.
acetate.
routes
]633].
acetate:
12 refs.
a
[634].
[635]. gas to ethylene
glycol.
23 refs.
[636].
509
Syntheses gas
of oxygen-containing
in the presence
Metal
carbonyls
Homogeneous 27 refs.
organic
of Rh catalysts.
in phase
and phase
transfer
transfer
compounds
77 refs.
catalysis.
catalyzed
from
synthesis
[6371. 102 refs.
16381.
carbonylation
reactions.
[6391.
Reactivity
of CO in transition
Catalytic
fixation
of carbon
metal dioxide
complexes. by metal
147 refs. complexes.
r6401. 274 refs.
[6411. Reversible
binding
complexes 33 refs.
containing
of transition
initiators
78 refs.
complexes
of Rh(1).
metals
of radical
in conjugation
reduction
with
hydrogen
of trichloromethyl
donors
compounds.
[634].
Syntheses metal
bis ditertiaryphosphine
by cationic
[642].
Carbonyls -
of H2, 02, and CO, and catalysis
and catalytic
complexes.
Supported
actions
25 refs.
metal
complexes
of organosilicon
polymer-supported
[6441. as hydrogenation
catalysts.
206 refs.
[645]. Mechanism tions.
and
stereochemistry
Asymmetric
catalytic
tioselection.
112 refs.
Enantioselective 73 refs. Chiral
hydrogenation:
40 refs.
The applicability tion.
of asymmetric
catalytic
hydrogena-
[646]. mechanism
and origin
of enan-
[6471.
of asynnnetric homogeneous
catalytic
hydrogena-
[6481. catalysis
with
transition
metal
complexes.
[649].
ligands
Application
of organometallic
tion of L-DOPA.
References p. 5 14
for asymmetric
13 refs.
catalysis. catalysis
[651].
163 refs.
c6501.
to the commercial
produc-
Complex the
reducing
agents:
their
19 refs.
field of carbonylations.
Selective
reduction
HRh(PPh3)4.
catalyzed
Catalyzed Effect
synthesis.
electro-organic
electrochemistry.
compounds
Activation
in
in the presence
and their
applications
of
oxidation
type,
-
in electro-
[654]. a modern
chapter
of organic
[655]. of olefinic
reaction
on epoxide
oxygen
and other
53 refs.
by metal
II.
oxidizable
16561.
complexes
oxidation.
as catalysts
hydrocarbons.
conditions
yield.
of liquid-phase
Metalloporphyrins
acid
64 refs.
201 refs.
of molecular
the mechanism
outcome
[652].
by formic
syntheses
liquid-phase
of catalyst
organic
and their
[653].
of Ni compounds
organic
Indirect
of aldimines
9 refs.
Electrochemistry
applications
and its role
119 refs.
in autoxidation
in
!657].
processes.
170 refs.
[658]. Metalloporphyrin-catalyzed
oxygenation
of hydrocarbons.
184 refs.
[659]. Dependence
of activity
and selectivity
for hydroperoxide
epoxidation
carrier.
[66O].
8 refs,
of olefins
The discovery
of the asymmetric
The discovery
of titanium-catalyzed
26 refs.
of asymmetric
catalysts.
104 refs.
Asymmetric
epoxidation
105 refs.
Synthetic 69 refs. A short metric
catalysts
on the structure
epoxidation.
22 refs.
asymmetric
of the
16611.
epoxidation.
[662].
On the mechanism
tion.
of immobilized
aspects
epoxidation
with
titanium-tartrate
16631. of allylic
alcohols:
the Sharpless
epoxida-
[664]. and applications
of asymmetric
epoxidation.
[665]. route
to chiral
oxidation.
sulfoxides
25 refs.
[666].
using
titanium-mediated
asym-
511 83 refs. [6671.
25 Years in the organic chemistry of palladium. The chemistry of activated bleomycin.
58 refs. [6681.
Toward functional models of metalloenzyme active sites: analogue reaction systems of MO 0x0 transferases. Biomimetic oxidations catalyzed by copper.
50 refs. [6691. 49 refs. [6701.
Biomimetic oxidation of hydrocarbons and drugs by metalloporphyrinit systems.
41 refs. [671].
Biological strategies for the manipulation of dioxygen. The chemistry of cytochrome P-450.
34 refs. [672].
List of Abbreviations
acac
acetylacetonate
AS
Annual Survey on Hydroformylation, Reduction, and Oxidation
BPPM
see Fig. (25a)
bpY chiraphos
2,2'-bipyridine see AS 1985, Fig.(g)
COD
1,5-cyclooctadiene
Co(salen)
see Fig. (169)
Co(salpr)
see AS 1985,
CP
cyclopentadienyl
CY DET
cyclohexyl
Fig. (109)
diethyl tartrate
DIOP
see AS 1985,
dipamp
see AS 1985, Fig. (34)
dmgH
dimethylglyoxime
Fig. (31)
dppb
1,4-bis(diphenylphosphino)butane,
Ph2P(CH2)4PPh2
dppe
1,2-bis(diphenylphosphino)ethane,
Ph2PCH2CH2PPh2
dppm
bis(diphenylphosphino)methane,
dppp HD
1,5-hexadiene
HMPA
hexamethylphosphoric triamide
men NBD
menthyl norbornadiene
nmen
neomenthyl
References p. 5 14
Ph2PCH2PPh2
1,3-bis(diphenylphosphino)propane
Ph2P(CH2)3PPh2
512 OEP
2,3,7,8,12,13,17,18-octaethylporphyrinato
0.y.
optical
yield
phen
l,lO-phenanthroline
PY
pyridine
salen
N,N'-bis(salicylidene)-ethylenediamino
SIL
silica
st
stearate,
nC17H35C00
TDCPP
5,10,15,20-tetrakis(2,6-dichlorophenyl)oorphyrin~
TDMPP
5,10,15,20-tetrakis(2,6-dimethylphenyl)porphyrinato
tetpy
2,2':6',2":6",2"'
TMP
5,10,15,20-tetramesitylporphyrinato
-tetrapyridine
TPP
5,10,15,20-tetraphenylporphyrinato
TPP-Me-p
5,10,15,20-tetrakislp-tolyl)porphyrinato
TPP-OMe-p
5,10,15,20-tetrakis(E_methoxyphenyl>porphyrinato
trpy Ts
p-toluenesulfonyl
Z
benzyloxycarbonyl,
Metal
Ti
2,2': 6'2"-terpyridine
79, 183-185, 538
Zr
41, 122,
157,
V
433,
Nb
122
Ta
122
Cr
43, 112-114,
440,
586-588, 100,
200,
109,
1, 190, 403,
562-566, 274,
Re
68, 116,
500,
546,
299,300,
501, 539, 544, 545
372,
409, 510-514,
547-561,
618
200, 223,
293, 343, 354,
502, 503, 515, 343, 344,
371,
540-543,
408, 442-446, 589, 606,
447, 448, 450, 473,
466
607, 616
475-477,
606
410-413, 590-593, 610 123,
473, 474, 495,
200, 258,
476,
494,
243
441, 449,
299, 317,
405,
Tc
254, 257, 265, 280, 316, 429-439,
242,
255, 261,
541, 542, Mn
251,
606, 617,
473, 475, W
PhCH200C-
index
504-506,
MO
(tosyl) p-CH3C6H4S02-
218
318, 320, 450-457, 608,
321, 323-325, 476, 496,
609, 624
357, 382, 383,
497, 516-523,
529,
513
Fe
RU
OS
co
91-93,
98, 102, 267,
406,
410, 412-419,
287, 301,
126, 127,
193,
302, 318, 355-357, 457-468,
479-482,
567-571,
578, 594-599,
7, 9-12,
23, 24, 44, 45, 62, 65-71,
611-613,
117, 124,
128-133,
229,
230, 234,
239, 241, 275, 286,
375,
384,
524,
525, 570,
398, 399,
180-182,
498,
76, 78-82,
469-473,
6, 13, 25-31,
43, 45, 47, 48, 61, 63-68,
370, 372, 376,
530-532,
546,
8, 12-20,
22-24,
197-199,
244-247,
483-486,
490,
471, 487-490,
343,
383, 385-390,
70-73,
77, 81, 83,
231, 233, 347-350,
401,
240, 256,
357,
358,
416, 450,
575, 576, 583 32-42,
83, 89, 100, 103-106, 194,
210, 225,
304, 323-336,
360-364,
224,
346, 374,
603, 614
176, 188-190, 299,
84, 93-102,
201-209,
205, 470,
574, 596,
136-138,
564,
621-623
508, 526-529,
270, 294,
262, 404,
624
297, 322, 345,
5, 23, 24, 84, 101, 134, 135, 187,
268,
383, 396,
499, 507,
186, 195,
407, 420-422,
597, 600-602,
237, 259, 260, 373,
619, 620,
116,
85-88,
Rh
110-115,
266,
208,
49-57,
118, 139-149,
211-215,
250, 269,
68, 69, 72-75,
219,
158-175,
230, 231,
275, 277, 279, 281,
78, 79, 82, 177-179,
191,
234-236,
282, 288, 305-308,
577 Ir
21, 23, 24, 93, 125, 247-249,
Ni
Pd
148, 149, 216,
134, 135,
150, 176,
295, 296, 303,
336,
580
104,
151-156,
108, 121,
272, 273,
276, 278,
338,
423-425,
Pt
2, 22, 46, 58-60,
cu
270, 271, 365-369, 500, 509,
Ag
342, 428
Ce
400,
sm
252, 253,
Eu
283, 298
428,
228, 230,
578
107, 119, 120,
351,
217, 225,
579,
162,
192-194,
220-222,
225,
289-292,
308-315,
319, 337,
491,
492, 499,
90, 156, 198,
383,
230, 238,
338-341, 391-395,
226,
533-536 320
352, 353, 357, 402,
359,
426, 427, 472,
568, 581,
604, 614, 615
483, 531,
537, 573, 582-585,
276, 298
264, 270,
284-286,
296, 311-315, 377-381,
194, 263,
605
493,
514 Lu
3, 298
Y, La, Nd, Gd, Er, Lu U
298
227
Transition
metals,
general
4, 93
References
1
(1986) 2
G.Li,
J.Am.Chem.Soc.
108
612. F-Ding,
F.Dai
(1986)
5911.
CA 105 3
L.Vers1ui.s and V.Tschinke,
T.Ziegler,
H.Rabaa, (1986)
and L.Zhang,
J.-Y.Saillard
Huaxue
and R.Hoffmann,
Xuebao
43 (1985)
J.Am.Chem.Soc.
878;
108
4327.
A.Sevin
and M.Fontecave,
K.A.Jorgensen
J.Am.Chem.Soc.
and R.Hoffmann,
J.L.Costa,
A.Demonceau,
P.Teyssie,
Acta
J.Am.Chem.Soc.
J.Drapier,
Chim.Hunq.
108 (1986)
108 (1986)
A.Hubert,
119 (1985)
3266.
A.Noel
1867.
and
147; CA 104 (1986)
132660. 7
I.W.Shim, CA 104
V.D.Mattera
(1986)
8
H.W.Bosch
9
Y.Kiso,
and W.M.Risen,
J.Catal.
94 (1985)
and B.B.Wayland,
M.Tanaka,
J.C.S.Chem.Commun.
H.Nakamura,
J.Organomet.Chem.
312
(1986)
T.Yamasaki
(1986)
357.
Y.Kiso
and K.Saeki,
J.Orqanomet.Chem.
309 (1986)
C26.
11
Y.Kiso
and K.Saeki,
J.Organomet.Chem.
303 (1986)
C17.
12
R.Whyman,
13
Am.Chem.Soc
900.
and K.Saeki,
10
(1986)
531;
19312.
.,Div.Pet.Chem.
31 (1986)
32; CA 104
226654.
T.Masuda,
K.Murata
and A.Matsuda,
Bull.Chem.Soc.Jpn.
59(1986)
1287. 14
G-Van (1986)
15
der
Lee and V.Ponec,
J.Catal.
99 (1986)
511; CA 105
45196.
W.M.H.Sachtler, 513; CA 105
D.F.Shriver
(1986)
45197.
and M.Ichikawa,
J.Catal.
99
(1986)
515
16
T.Masuda, K.Murata, T.Kobayashi and A.Matsuda, Bull.Chem. Soc.Jpn. 59 (1986) 2349.
17
H.Tanaka, Y.Hara, E.Watanabe, K.Wada and T.Onoda, J.Organomet.Chem. 312 (1986) C71.
18
M.Tamura, M.Ishio, T.Deguchi and S.Nakamura, J.Organomet. Chem. 312 (1986) C75.
19
E.Watanabe, Y.Hara, K.Wada and T.Onoda, Chem.Lett. (1986) 285.
20
E.Watanabe, K.Murayama, Y.Hara, Y.Kobayashi, K.Wada and T.Onoda, J.C.S.Chem.Commun.
21
(1986) 227.
T.Takano, T.Deguchi, M.Ishino and S.Nakamura, J.Organomet. Chem. 309 (1986) 209.
22
M.Rijper, M.Schieren and A.Fumagalli, J.Mol.Catal. 34 (1986) 173.
23
J.A.Marsella and G.Pez, J.Mol.Catal. 35 (1986) 65.
24
J.A.Marsella and G.P.Pez, Prepr.-Am.Chem.Soc.,Div.Pet.Chem 31 (1986) 22; CA 104 (1986) 188631.
25
J.Krupcik and D.Repka, Collect.Czech.Chem.Commun. 1808;
50 (1985
CA 104 (1986) 28196.
26
J.Kolena, Chem.Prum. 35 (1985) 300. CA 104 (1986) 129210.
27
V.Macek and R.Kubicka, Ropa Uhlie 28 (1986) 164; CA 105 (1986) 45198.
28
Y-Sun, D.Zhang, Z.Zhao, W.Zhai, Y.Ma, Z.Wang, Y-Ma and D.Li, Shiyou Huagong 15 (1986) 372; CA 105 (1986) 193293.
29
Yu.B.Kagan, O.L.Butkova, G.A.Korneeva and S.M.Loktev, Izv. Akad.Nauk SSSR, Ser.Khim. (1985) 1714; CA 105 (1986) 42292.
30
M.K.Markiewicz and M.C.Baird, Inorg.Chim.Acta 113 (1986) 95.
31
J.Collin, C.Jossart and G.Balavoine, Organometallics 5 (1986) 203.
32
K.Doyama, T.Joh, S.Takahashi and T.Shiohara, Tetrahedron Lett. 27 (1986) 4497.
33
S.Li, W.Yuan, D.Liu, W.Pan and J.Liu, Wuli Huaxue Xuebao 2 (1986) 77; CA 105 (1986) 135863.
34
A.J.Abatjouglu and D.R.Bryant,Arabian J.Sci.Eng. 10 (1985) 427; CA 105 (1986) 208282.
516 35
W.E.Smith,
G.R.Chambers,
G.E.Harrison 151; CA 105 36
A.M.Trzeciak
38
A.A.Bahsoun (1986)
and R.Ziessel,
P.Escaffre,
P.Kalck,
A.Thorez,
J.Mol.Catal.
Nouv.J.Chim.
P.Kalck,
J.
34 (1986)
9 (1985)
B.Besson,
J.Organomet.Chem. F.Serein
D.C.Park,
F.Senocq,
302
213.
225; CA 104
R.Perron
and
(1986) C17.
and A.Thorez,
C.Randrianalimanana, J.Mol.Catal.
K.Prbkai-Tatrai,
J.Mol.Catal.
36
A.Thorez, 35 (1986)
S.Tijrijsand B.Heil,
P.Kalck,
R.Choulaoun
213. J.Organomet.Chem.
315
231. Ind.Eng.Chem.Prod.Res.Dev.
E.R.Tucci, (1986)
44
Eldik,
349.
(1986) 43
and R.van
337.
and J.J.Ziolkowski,
and D.Gervais, 42
A.J.Dennis,
22 (1985)
13991.
(1986) 41
S.Aygen
J.J.Zidlkowski,
Y.Colleuille, 40
J.N.Cawse,
Chem.Ind,(Decker)
133314.
34 (1986)
Mol.Catal.
39
(1986)
A.M.Trzeciak,
37
R.C.Lindberg,
and D.R.Bryant,
25 (1986)
27; CA 104
111757.
E.M.Gordon
and R.Eisenberg,
J.Organomet.Chem.
306
(1986)
c53. 45
M.Hidai, (1986)
46
P.W.N.M.
van Leeuwen,
48
S.Zhang,
307
51
J.Mol.Catal.
35
J.M.Herman,
S.E.Moore,
K.D.Lavin
P.E.Garrou
P.J. Van Den Berg
H.Li,
B.He,
14 (1985)
Y.Luo
and H.Fu,
J.Organomet.
and H.R.Allcock,
and R.A.Dubois,
259; CA 105 (1986)
32 (1986)
Huaqonq
and J.H.G.
Organo-
460.
J.(Lausanne) J.San,
N.Wu,
R.L.Wife 31.
65.
P.E.Garrou,
19 (1985)
(1986)
A.Zhang,
5 (1986)
D.L.Hunter, Catal.
50
(1986)
R.A.Dubois, metallics
49
G.F.Roobeek,
J.C.S.Chem.Commun.
Y.Wang, Chem.
and Y.Uchida,
29.
Frijns, 47
Y.Koyasu
A.Fukuoka,
and J.J.F.Scholten,
101; CA 105
X.Yang,
X.Wang
390; CA 104
Appl.
96829.
(1986)
26116.
and Q.Zhou,
(1986)
Chem.Enq.
209125.
Shiyou
517
52
B.He, F.Zheng, J.Sun, H.Li, Q.Zhou, G.Liu, X.Yang and C.Fu, Cuihua Xuebao 6 (1985) 296; CA 104 (1986) 198737.
53
D.L.Hunter, S.E.Moore, A.R.Dubois, P.E.Garrou, Appl.Catal. 19 (1985) 275; CA 105 (1986) 60142.
54
F.R.Hartley, S.G.Murray and A.T.Sayer, J.Mol.Catal. 38 (1986) 295.
55
E.J.Rode, M.E.Davis and B.E.Hanson, J.Catal. 96 (1985) 563; CA 105 (1986) 60186.
56
R.J.Davis, J.A.Rossin and M.E.Davis, J.Catal. 98 (1986) 477; CA 105 (1986) 42230.
57
E.J.Rode, M.E.Davis and B.E.Hanson, J.Catal. 96 (1985) 574; CA 104 (1986) 185796.
58
C.Pan, Y.Zhao, Y.Chen, Zhongguo Kexue Jishu Daxue Xuebao 15 (1985) 439; CA 105 (1986) 208287.
59
J.K.Stille, Chem.Ind.(Decker) 22 (1985) 23; CA 104 (1986) 129560.
60
G.Parrinello, R.Deschenaux and J.K.Stille, J.Org.Chem. 51 (1986) 4189.
61
Z.Zhang, X.Wang, W.Zhao, S.Zhang, Y.Fang and B.Na, Huaxue Xuebao 44 (1986) 506; CA 105 (1986) 90126.
62
G.Braca, A.M.Raspolli Galletti and G.Sbrana, Prepr.-Am.Chem. sot., Div.Pet.Chem. 31 (1986) 104; CA 105 (1986) 8303.
63
Y.Sugi, K.Takeuchi, H.Arakawa, T.Matsuzaki and K.-I.Bando, Cl Mol.Chem. 1 (1986) 423.
64
E.Lindner, C.Scheytt and P.Wegner, J.Organomet.Chem. 308 (1986) 311.
65
W.Strohmeier, H.HBcker and G.Sommer, Cl Mol.Chem. 1 (1986) 475.
66
E.Lindner, H.A.Mayer and P.Wegner, Chem.Ber. 119 (1986) 2616.
67
E.Lindner, A.Sickinger and P.Wegner, J.Organomet.Chem. 312 (1986) C37.
68
T.Matsuzaki, Y.Sugi, H.Arakawa, K.Takeuchi, K.Bando and N.Isogai, Chem.Ind.(London)(l985)555; CA 104 (1986) 148255.
518 69
314
metal.Chem. 70
71
(1986)
G.Bitsi
G.Jenner,
(1986)
K.Watanabe,
K.Kudo,
J.Organo-
227. Appl.Catal.
24 11986)
100106. S.Mori
and N.Sugita,
Bull.Chem.Soc.Jpn.
2565. F.Hugues
D.Commereuc,
Y.Chauvin, Catal.
and T.A.Pakkanen,
and P.Andrianary,
319; CA 105
59 (1986) 72
K.Karjalainen
J.Purdianinen,
34 (1986)
73
M.Marchionna
74
T.Okano,
and D.Prouteau,
J.Mol.
275.
and G.Longoni,
J.Mol.Catal.
H.Konishi
M.Makino,
35 (1986)
and J.Kiji,
107.
Chem.Lett.
(1985)
1793. 75
T.Okano,
H.Ito,
H.Konishi
and J.Kiji,
Chem.Lett.
(1986)
1731. 76
J.R.Zoeller,
77
R.W.Wegman
78
E.Drent,
79
G.Braca, Catal.
J.Mol.Catal. and D.C.Busby,
37 (1986)
377.
J.C.S.Chem.Commun.
J.Mol.Catal.
37 (1986)
93.
A.M.Raspolli
Galletti,
G.Sbrana
34 (19861
J.R.Zoeller,
81
G.Jenner
and P.Andrianary,
a2
E.Drent,
Prepr.-Am.Chem.Soc.,Div.Pet.Chem.
a3
a4
a5
86
J.Mol.
37 (1986)
117.
J.Orqanomet.Chem.
307 (1986) 31 (1986)
263.
97;
and G.Jenner,
J.Organomet.Chem.
310
115.
D.S.Sarratt (1986)
and F.Zanni,
188634.
H.Kheradmand
G.Bitsi, (1986)
J.Mol.Catal.
(1986)
332.
183.
80
CA 104
(1986)
and D.J.Cole-Hamilton,
J.Organomet.Chem.
306
c41.
M.S.Borovikov
and V.A.Ryabkov,
CA 104
224526.
(1986)
I.Kovacs,
F.Ungvary
Kinet.Katal.
and L.Mark6,
27 (1986)
Organometallics
319;
5 (1986)
209. a7
F.Ungvbry
88
R.A.Dubois and P.E.Garrou,
and L.Mark6,
Organometallics
5 (1986)
Organometallics
2341.
5 (1986)
466.
519 89
E.V.Slivinskii,
Yu.B.Kagan,
R.A.Aranovich, Neftekhimiya 90
A.Scrivanti,
91
C.Pac,
92
93
94
A.Berton,
L.Toniolo
(1986)
S.Nakamura,
90 (1986)
5244: CA 105
97
(1986)
T.Venalainen,
E.Iiskola, J.Mol.Catal.
4140.
H.Ishida,
K.Tanaka, 5 (1986)
98
D.C.Gross
and P.C.Ford,
99
Y.Shvo
112 101
T.A.Pakkanen
and
and T.T.Pakkanen,
T.T.Pakkanen
O.Weir
M.Morimoto
and E.Iiskola,
and J.G.Vos,
Inorg.Chem.
and T.Tanaka,
J.Am.Chem.Soc. J.Organomet.Chem.
G.Zassinovich
(1986)
T.A.Pakkanen 293.
Organo-
724.
and D.Czarkie,
G.Clauti,
J.Phys.Chem.
314 (1986) C49.
metallics
100
and S.Kagawa,
305.
W.Hinrichs,
25 (1986)
J.C.S.
159429.
34 (1986)
T.A.Pakkanen,
J.G.Haasnoot,
J.Organo-
and H.Sakurai,
J.Pursiainen,
E.Iiskola, 34 (1986)
J.Organometal.Chem. 96
S.Yanagida
H.Kusano
T.T.Pakkanen,
T.Venalainen,
and C.Botteghi,
1115.
M.Iwamoto,
T.Venalainen,
and S.M.Loktev, 56974.
369.
T.Matsuo,
(1986)
J.Mol.Catal. 95
791; CA 104 (1986)
K.Miyake,
Chem.Commun.
G.A.Korneeva,
N.N.Rzhevskaya
25 (1985)
314
metal.Chem.
V.I.Kurkin,
I.G.Fal'kov,
and G.Mestroni,
108 315
(1986)
6100.
(1986) C25.
Inorg.Chim.Acta
103.
R.A.Sanchez-Delgado
and A.Oramas,
J.Mol.Catal.
36 (1986)
283. 102
C.Crotti,
S.Cenini,
J.C.S.Chem.Commun. 103
T.Kitamura CA 104
B.Rindone, (1986)
and T.Joh,
(1986)
S.C.Shim,
K.N.Khoi
105
K.Kaneda,
M.Kobayashi,
106
Kaishi
K.Takeuchi, Cl Mol.Chem.
and F.Demartin,
Nippon
Kagaku
Kaishi
(1985)
473;
Chem.Lett.
(1986)
1149.
108626.
104
Kagaku
S.Tollari
784.
and Y.K.Yeo,
(1985)
Y.Sugi,
T.Imanaka
and S.Teranishi,
494; CA 104 (1986) T.Matsuzaki,
1 (1986)
407.
Nippon
147887.
H.Arakawa
and K.-I.Bando,
520 107
P.Giannoccaro (1986)
108
N.K.Eremenko
A.I.Min'kov, SSSR
109
and E.Pannacciulli,
Inorg.Chim.Acta
117
69.
283
(1985)
and O.A.Efimov,
160; CA 105
R.Sapienza,
W.Slegeir
249; CA 104
(1986)
(1986)
Dokl.Akad.Nauk
6243.
and D.Mahajan,
Polyhedron
5 (1986)
209135.
110
K.Ogura
and I.Yoshida,
J.Mol.Catal.
34 (1986)
309.
111
K.Ogura
and I.Yoshida,
J.Mol.Catal.
34 (1986)
67.
112
K.Ogura
and M.Takagi,
Electrochem. 113
K.Ogura
(1986)
(1986)
(1986)
J.C.S.Dalton
Trans.
50672. (1985)
2499:
185795. 16 (1986)
J.Appl.Electrochem.
K.Ogura,
Chem.Interfacial
359; CA 105
and S.Yamazaki,
CA 104 114
201
J.Electroanal
732; CA 105 (1986)
160782. 115
M.Nakazawa,
Y.Mizobe,
Y.Matsumoto,
Bull.Chem.Soc.Jpn.
M.Hidai, 116
H.Kukkanen
117
R.Maidan,
and I.Willner,
T.Fukaya,
M.Kodaka
118
Hokoku 119
and T.Pakkanen,
81 (1986)
D.J.Pierce
120
and M.Sugiura,
197 (1986)
C.L.Bailey, Chim.Acta
121
Y.Fujiwara,
Tetrahedron
Lett.
123
W.D.Jones
and M.Fan,
124
H.Suzuki,
D.H.Lee,
Chem.
(1986) C45.
126
(1986)
Kagaku
D.P.Rillema
H.Taniguchi,
and R.M.Zubyk,
C.J.Cameron,
R-Davis,
108
(1986) L43.
(1986)
Gijutsu
8100.
Kenkyusho
180378.
J.Electroanal.Chem.Interfacial
27 !1986)
W.A.Nugent
E.Guittet,
and
77520.
and R.Nowak,
Inorg.
116 (1986) L45.
122
125
114
317; CA 104 (1986)
R.D.Bereman,
Y.Morimoto,
317
J.Am.Chem.Soc.
255; CA 105 (1986)
M.Tezuka
809.
Inorg.Chim.Acta
and D.Pletcher,
Electrochem.
Y.Uchida,
59 (1986)
Organometallics
H.Felkin,
N.M.S.Khazaal 1387.
25 (1986) 5 (1986)
and Y.Moro-oka,
T.Fillebeen-Khan,
J.C.S.Chem.Commun.
and Y.Nagano,
1809.
Inorg.Chem.
N.Oshima
Y.Hori
4604.
1057.
J.Organomet.
N.J.Forrow
and
(1986) 801.
and V.Maistry,
J.C.S.Chem.Commun.
521
125
'C.J.Cameron, H.Felkin, T.Fillebeen-Khan, N.J.Forrow and EdGuittet, J.C.S.Chem.Commun. (1986) 801.
126
R.Davis, N.M.S.Khaz.aal and V.Maistry, J.C.S.Chem.Commun. (1986) 1387.
127
H.Inoue, Y.Nagao and E.Haruki, Chem.Express 1 (1986) 165; CA 105 (1986) 152489.
128
C.Bello,L.L.Diosady, W.F.Graydon and L.J.Rubin,JAOCS, J. Am.Oil Chem.Soc. 62 (1985) 1587; CA 104 (1986) 18813.
129
J.A.Smieja, J.E.Gozum and W.L.Gladfelter, Organometallics 5 (1986) 2154.
130
J.L.Zuffa, M.L.Blohm and W.L.Gladfelter, J.Am.Chem.Soc. 108 (1986) 552.
131
B.He, K.Teng, J.Sun and H.Li, Yingyong Huaxue 2 (1985)(4) 31; CA 104 (1986) 96414.
132
Y.Doi, K.Yano, A.Yokota,H.Miyake and K.Soga, Int.Congr. Catal., 8th (1984) IV689; CA 105 (1986) 121563.
133
L.N.Lewis, J.Am.Chem.Soc. 108 (1986) 743.
134
J.L.Zuffa and W.L.Gladfelter, J.Am.Chem.Soc. 108 (1986) 4669.
135
M.Castiglioni, R.Giordano, E.Sappa, A.Tiripicchio and C.M.Tiripicchio, J.C.S.Dalton Trans. (1986) 23; CA 105 (1986) 97657.
136
L.I.Gvinter, L.N.Suvorova, S.S.Danielova and L.Kh.Freidlin Zh.Org.Khim. 22 (1986) 79; CA 105 (1986) 209215.
137
G.C.Pillai, J.W.Reed and E.S.Gould, Inorg.Chem. 25 (1986) 4734.
138
G.C.Pillai and E.S.Gould, Inorg.Chem. 25 (1986) 4740.
139
E.E.Nifantyev, A.T.Teleshev, G.M.Grishina and A.A.Borisenko, Phosphorus Sulfur 24 (1985) 333; CA 104 (1986) 60958.
140
M.M.Taqui Khan, B.Taqui Khan, S.Begum and S.Mustafa Ali J.Mol.Catal. 34 (1986) 283.
141
J.A.Heldal and E.N.Frankel, JAOCS, J.Am.Oil Chem.Soc. 62 (1985) 1117; 104 (1986) 148064.
522 142
S.A.Preston,
143
M.Zuber, (1986)
144
W.A.Szuberla
J.Azran,
O.Buchman,
V.N.Kalinin,
SSSR,
147
F.Lu,
and F.P.Pruchnik,
I.Amer
O.A.Mel'nik,
977.
J.Mol.Catal.
and J.Blum,
J.Mol.Catal.
(1985)
38
34
D-Wang
Y.Wang,
and
(1986)
V.Zbirovsky
and M.Capka,
836; CA 105
(1986)
Khan,
T.M.Frunze,
and V.Z.Sharf,
2442: CA 105 (1986)
154; CA 104
M.M.Taqui
A.A.Sakharova,
N.V.Borunova
Ser.Khim.
(1986) 148
and
(1986)
229.
L.I.Zakharkin,
146
J.C.S.Chem.Commun.
309.
(1986) 145
P.Palma-Ramirez
D.C.Cupertino,
D.J.Cole-Hamilton,
Y.Yu,
Gaofenzi
Izv.Akad.Nauk 226929.
Tongxun
(1985)
19914. Collect.Czech.Chem.Commun.
(1986)
B.Taqui
51
226955.
Khan and S.Begum,
J.Mol.Catal.
34
9.
149
R.H.Crabtree
150
K.M.Ho,
and M.W.Davis,
M.C.Chan
J.Orq.Chem.
and T.Y.Luh,
51 (1986)
Tetrahedron
Lett.
2655.
21 (1986)
5383. 151
L.V.Mironova,
Yu.S.Levkovskii,
N.A.Ivanova,
G.V.Ratovskii,
Koord.Khim. 152
11 (1985)
E.A.Bekturov,
L.B.Belykh,
E.I.Dubinskaya
1689; CA 104 (1986)
S.E.Kudaibergenov,
A.K.Zharmagametova, Makromol.Chem.,
Commun.
and F.K.Shmidt, 40520.
D.V.Sokol'skii,
S.G.Mukhamedzhanova
Rapid
G.V.Lobza,
7 (1986)
and A.Sh.Kuanyshev, 187; CA 104 (1986)
206675. 153
E.A.Bekturov,
S.E.Kudaibergenov,
D.V.Sokolskii,
A.K.Zharmagambetova
React.Polym.,Ion (1986) 154
Exch.,
G.A.Sytov,
and N.S.Nametkin,
155
(1986)
K.R.Kumar, Catal., 129298.
and N.V.Anisimova,
Sorbents
4 (1985)
49; CA 104
110900.
V.N.Perchenko,
CA 104
S.S.Saltybaeva,
R.Sh.Abubakirov,
Dokl.Akad.Nauk.SSSR
T.O.Omaraliev
282 (1985)
109;
129521.
B.M.Choudary,
M.Z.Jamil
(Proc.Natl.Symp.Catal.)
and G.Thyaqarajan,
7th (1985j 71; CA 104
Adv. (1986)
523
156
I.Feinstein-Jaffe and A.Efraty, J.Mol.Catal. 35 (1986) 285.
157
R.Choukroun, M.Basso-Bert and D.Gervais, J.C.S.Chem.Commun. (1986) 1317.
158
F.Pruchnik, B-R-James and Kvintovics, Can.J.Chem. 64 (1986) 936.
159
H.Takaya, K.Mashima, K.Koyano, M.Yagi, H.Kumobayashi, T.Taketomi, S.Akutagawa and R.Noyori, J.Org.Chem. 51 (1986) 629.
160
J.M.Brown, L.Cutting, P.L.Evans and P.J.Maddox, Tetrahedron Lett. 27 (1986) 3307.
161
H.Brunner, A.Knott, M.Kunz and E.Thalhammer, J.Organomet. Chem. 308 (1986) 55.
162
C.Fuganti, P.Grasselli, L.Malpezzi and P.Casati, J.Org. Chem. 51 (1986) 1126.
163
J.M.Nuzillard, J.C.Poulin and H.B.Kagan, Tetrahedron Lett. 27 (1986) 2993.
164
F.Alario, Y.Amrani, Y.Colleuille, T.P.Dang, J.Jenck, D.Morel and D.Sinou, J.C.S.Chem.Commun. (1986) 202.
165
T.Minami, Y.Okada, R.Nomura, S.Hirota, Y.Nagahara and K.Fukuyama, Chem.Lett. (1986) 613.
166
W.Zhong, R.Li, J.Zhang, L.Weng, Y.Shi and H.Feng, Tianjin Daxue Xuebao (1985) (2) 99; CA 105 (1986) 42927.
167
D.Sinou and Y.Amrani, J.Mol.Catal. 36 (1986) 319.
168
S.Saito, Y.Nakamura and Y.Morita, Chem.Pharm.Bull. 33 (1985) 5284; CA 105 (1986) 79250.
169
A.Kinting and H.-W.Krause, J.Organomet.Chem. 302 (1986) 259.
170
U.Nagel, E.Kinzel, J.Andrade and G.Prescher, Chem.Ber. 119 (1986) 3326.
171
U.Nagel and E.Kinzel, Chem.Ber. 119 (1986) 1731.
172
U.Nagel and E.Kinzel, J.C.S.Chem.Commun.
173
M.Yamashita, M.Kobayashi, M.Sugiura, K.Tsunekawa,
(1986) 1098.
T.Oshikawa, S.Inokawa and H.Yamamoto, Bull.Chem.Soc.Jpn. 59 (1986) 175.
524 114
R.Selke
175
R.Selke,
176
W.Guo,
Y.Chen
and Y.Ma,
CA 104
(1986)
207811.
177
and H.Pracejus,
178
D.G.Allen,
183
184
186
188
P.Frediani,
J.Am.Chem.Soc.
L.A.Paquette,
G.Pfeiffer
and
Organometallics
5
Tetrahedron
Yi Hsiao,
Lett.
J.A.McKinney,
P.Le Coupanec
(1985)
T.Ohta
and
Lett.
and
27 (1986)
5599.
and P.H.Dixneuf,
J.Orqanomet.
C35.
T.Feng
and Y.Zhou,
CA 104
(1986)
M.O.Albers,
173009.
(1986) 7117. M.L.McLaughlin
B.Demerseman,
and M.Bianchi,
(1986)
M.Kitamura,
108
Tetrahedron
287
G.Menchi
53; CA 105
A.L.Rheingold,
Tongji
Daxue
Xuebao
(1984)
(4) 79;
19248.
E.Sinqleton
and M.M.Viney,
J.Mol.Catal.
34
235.
R.A.Sanchez-Delgado,
A.Andriollo,
V.Leon
and J.Espidel,
CA 104
(1986)
L.I.Cvinter,
J.C.S.Dalton
E.Gonzales, Trans.
N.Valencia,
(1985)
1859;
33647. V.M.Ignatov,
and V.S.Sharf,
V.Yu.Egorova, Neftekhimiya
L.N.Suvorova, 26 (1986)
37; CA 105
190426.
H.Kanai,
Y.Watabe
and T.Nakayama,
Rull.Chem.Soc.Jpn.
59
1277.
J.F.Garst, (1986)
312
93.
U.Matteoli,
68 (1986)
M.Ohta,
(1986)
190
(9) 16;
5497.
R.Noyori,
(1986)
G.Buono,
317 (1986)
and G.Simonneaux,
H.Takaya,
P.S.Belov
189
(1985)
J.Organomet.Chem.
and D.L.Wood,
P.Le Maux
F.Piacenti,
(1986) 187
Tongbao
213.
1009.
V.Massoneau,
Chem. 185
Huaxue
F.Petit,
S.B.Wild,
Chim.Ind.(Milan) 182
227.
and F.Petit,
A.Mortreux,
27 (1986) 181
37 (1986)
J.Organomet.Chem.
(1986) 180
A.Mortreux
37 (1986)
375.
A.Karim, C.Siv,
179
J.Mol.Catal.
A.Karim, (1986)
J.Mol.Catal.
T.M.Bockman
1689.
and R.Batlaw,
J.Am.Chem.Soc.
108
525 191
V.Zbirovsky, H.J.Kreuzfeld and M.Capka, React.Kinet.Catal. Lett. 29 (1985) 243; CA 104 (1986) 231278.
192
O.P.Parenago, G.M.Cherkashin and L.P.Shuikina, Neftekhimiya 25 (1985) 589; CA 105 (1986) 133300.
193
R.V.Honeychuck, M.O.Okoroafor, L.-H.Shen and C.H.Brubaker, Organometallics 5 (1986) 482.
194
E.Bayer and W.Schumann, J.C.S.Chem.Commun.
(1986) 949.
195
V.F.Pechenkina, R.A.Rustambekova, B.Zh.Zhanabeev and A.M.Ashirov, Izv.Vyssh.Uchebn.Zaved.,Khim.IZhim.Tekhnol. 28 (1985) 59; CA 105 (1986) 114630.
196
V.F.Pechenkina, D.V.Sokol'skii, B.Zh.Zhanabaev and A.M.Ashirov, Izv.Vyssh.Uchebn.Zaved.,Khim.Khim.Tekhnol. 28 (1985) 54; CA 105 (1986) 60325.
197
I.Amer, H.Amer, and J.Blum, J.Mol.Catal. 34 (1986) 221.
198
A.G.Dedov, A.S.Loktev, V.S.Pshezhetskii and E.A.Karakhanov, Neftekhimiya 25 (1985) 452; CA 105 (1986) 190506.
199
E.A.Karakhanov, E.B.Neimerovets, V.S.Pshezhetskii and A.G.Dedov, Khim.Geterotsikl.Soedin.
(1986) (3) 303;
CA 105 (1986) 23811. 200
P.A.Tooley, C.Ovalles, S.C.Kao, D.J.Darensbourg and M.Y.Darensbourg, J.Am.Chem.Soc. 108 (1986) 5465.
201
M.Tanaka, T.Sakakura, T.Hayashi and T.-A.Kobayashi, Chem. Lett. (1986) 39.
202
K.Hotta, Nippon Kagaku Kaishi (1985) 674; CA 104 (1986) 6028.
203
T.Suarez, B.Fontal and D.Garcia, J.Mol.Catal. 34 (1986) 163.
204
Y.Shvo, D.Czarkie, Y.Rahamin and D.F.Chodosh, J.Am.Chem. sot.
205
108 (1986) 7400.
R.A.Sanchez-Delgado, N.Valencia, R.-L.Marquez-Silva, A.Andriollo and M.Medina, Inorg.Chem. 25 (1986) 1106.
206
U.Matteoli, G.Menchi, M.Bianchi and F.Piacenti, J.Organomet.Chem. 299 (1986) 233.
207
U.Matteoli, G.Menchi, M.Bianchi, P.Frediani and F.Piacenti, Gazz.Chim.Ital. 115 (1985) 603; CA 104 (1986) 224426.
526 208
J.F.Knifton
209
Y.Ishii, Lett.
211
S.T&zos,
213
214
and H.Alper,
T.Kogure (1986)
H.Takahashi,
215
K.Tani, (1986)
216
217
Acta
Chim.Hunq.
119
208285. Organometallics
and Y.Yoda,
5 :1986)
Org.Synth.
63 (1985)
1909. 18;
Lett.
M.Chiba,
27 (1986) Y.Tatsuno
E.Tanigawa,
T.Morimoto
and K.Achiwa,
4477. and S.Otsuka,
Chem.Lett.
737.
E.Farnetti,
M.Pesce,
M.Graziani,
J.C.S.Chem.Commun.
(1986)
G.I.Korenyako,
J.Kaspar,
I.G.Iovel
Yu.Sh.Goldberg, Commun.
218
Tetrahedron
68661. M.Hattori,
Tetrahedron
387.
823.
and L.Markd,
135; CA 105 (1986)
I.Ojima, CA 104
and S.Yoshikawa,
59 (1986)
L.Kollar
B.Heil,
H.A.Zahalka
1 (1986)
365.
Bull.Chem.Soc.Jpn.
K.Mita,
(1985)
Cl Mol.Chem.
M.Saburi
T.Ikariya,
27 (1986)
210
212
and J.J.Lin,
R.Spogliarich (1986) 746.
and M.V.Shymanska,
J.C.S.Chem.
286. O.M.Negomedzyanova,
V.M.Belousov,
and
K.V.Kotegov
22 (1984)
Katal.Katal.
and
98; CA 104
(1986)
50596. 219
E.G.Leelamani, Adv.Catal. (1986)
220
221
222
(Proc.Natl.Symp.Catal.)
P.K.Santra
(1985)
Ser.Khim.
and M.V.Klyuev,
(1985)
97; CA 104
C.J.Casewit,
D.E.Coons, DuBois,
CA 104
L.L.Wright,
G.Siiss-Fink and G.Herrmann,
225
W.Oppolzer, R.J.Mills 183.
SSSR,
Ser.
E.S.Levitina, Izv.Akad.Nauk.SSSR,
(1986)
Organometallics
224
224414.
171933.
E.I.Karpeiskaya,
2157;
(1986)
Izv.Akad.Nauk
(1986)
and L.N.Kaigorodova,
(1985)
M.Rakowski
(1986)
and G.K.N.Reddy,
Proc.Indian Natl.Sci.
538; CA 104
1716; CA 105
E.I.Klabunovskii, L.F.Godunova
223
7th
and C.R.Saha,
Part A 51 (1985)
A.D.Pomogailo, Khim.
V.Gayathri
129299.
P.Khandual, Acad.,
N.Shashikala,
207626. W.K.Miller
5 (1986)
Angew.Chem.
and
951.
98 (1986)
and M.Reglier, Tetrahedron
568.
Lett.
27
527 226
R.M.Williams, D.Zhai and P.J.Sinclair, J.Org.Chem. 51 (1986) 5021.
227
G.B.Deacon, T.D.Tuong and G.R.Franklin, Inorg.Chim.Acta l_ll (1986) 193.
228
R.H.Grabtree, M.J.Burk, R.P.Dion, E.M.Holt, M.E.Lavin, S.M.Morehouse, C.P.Parnell and R.J.Uriarte, Chem.Ind. (Decker) 22 (1985) 37; CA 105 (1986) 24438.
229
I.Minami, M.Yamada and J.Tsuji, Tetrahedron Lett. 27 (1986) 1805.
230
T.Yamakawa, H.Miyake, H.Moriyama, S.Shinoda and Y.Saito, J.C.S.Chem.Commun.
231
(1986) 326.
S.K.Tyrlik, A.Korda and A.Gieysztor, J.Mol.Catal. 34 (1986) 313.
233
s.wu, F.Luo, Y.Teng and G.Li, Yingyong Huaxue 2 (1985) (2) 43; CA 104 (1986) 148602.
234
Y.Ishii, K.Osakada, T.Ikariya, M.Saburi and S.Yoshikawa, J.Org.Chem. 51 (1986) 2034.
235
Y.Ishii, K.Suzuki, T.Ikariya, M.Saburi and S.Yoshikawa, J.Org.Chem. 51 (1986) 2822.
236
Y.Ishii, I.Sasaki, T.Ikariya, M.Saburi and S.Yoshikawa, Nippon Kagaku Kaishi (1985) 465; CA 104 (1986) 129208.
237
C.E.Castro, M.Jamin, W.Yokoyama and R.Wade, J.Am.Chem.Soc. 108 (1986) 4179.
238
C.-M.Che and W.M.Lee, J.C.S.Chem.Commun. (1986) 512.
239
A.Basu and K.R.Sharma, J.Mol.Catal. 38 (1986) 315.
240
M.Onishi, K.Hiraki, S.Kitamura and Y.Ohama, Nippon Kagaku Kaishi (1985) 400; CA 104 (1986) 108768.
241
D.Milstein, J.Mol.Catal. 36 (1986) 387.
242
H.Matsushita and S.Ishiguro, Agric.Biol.Chem. 49 (1985) 3071; CA 104 (1986) 68512.
243
Y.Ishii, T.Nakano, A.Inada, Y.Kishigami, K.Sakurai and M.Ogawa, J.Org.Chem. 51 (1986) 240.
244
P.Kvintovics, B.R.James and B.Heil, J.C.S.Chem.Commun. (1986) 1810.
528 245
35 (1986)
Catal. 246
C.Botteghi,
H.W.Krause
306
G.Delogu,
304
M.Graziani
J.Kaspar,
J.Organomet.Chem. 248
G.Chessa,
J.Organomet.Chem.
R.Spogliarich,
and M.Valderrama,
J.Mol.
161.
G.Chelucci,
F.Soccolini, 247
M.Martinez
I.Carkovic,
R.Sariego,
(1986)
and A.K.Bhatnagar,
S.Gladiali
and
(1986) 217. and F.Morandini,
407. J.Organomet.Chem.
302
(1986)
265. 249
M.J.Fernandez,
M.A.Esteruelas,
J.Organomet.Chem. 250
S.I.Hommeltoft, 108
251
(1986)
J.L.Atwood
G.A.Molander
253
G.A.Molander, (1986)
(1986)
E.W.Colvin
256
FArena,
J.G.Abdo
25 (1986)
A.Sera,
J.Am.Chem.Soc.
Inorg.Chem.
25
51 (1986)
and G.Hahn,
2596.
J.Org.Chem.
51
Anal.Biochem.
J.C.S.Chem.Commun.
A.Chiesi-Villa
154
(1986)
and C.Guastini,
1084. Inorg.
4589. T.Yoneda
697; CA 105 (1986)
K.Behari (1986)
and C.Hamilton, (1986) 221619.
S.Fukumoto,
R.S.Varma,
M.Varma
and H. Yamada,
24
225912.
and G.W.Kabalka,
(1986)
Heterocycles
Synth.Commun.
15 (1985)
190560.
and M.Gautam,
Oxid.Commun.
8 (1985j
237; CA 105
133169.
260
H.Alper
261
E.W.Colvin
262
H.Inoue
263
Y.Fort, (1986)
J.Org.Chem.
Belle
and S.Cameron,
1325; CA 105 259
B.E.La
C.Floriani,
(1986) 258
and R.Eisenberg,
and G.D.Stucky,
and G.Hahn,
559; CA 104
255
257
and L.A.Oro,
5259.
H.A.Akers,
Chem.
D.H.Berry
M.Covarrubias 343.
98.
252
254
(1986)
5345.
D.R.Corbin, (1986)
316
and F.Sibtain,
J.Organomet.Chem.
and S.Cameron,
and T.Nagata, R.Vanderesse 5487.
285
J.C.S.Chem.Commun.
J.C.S.Chem.Commun. and P.Caubere,
(1985)
225.
(1986)
1642.
(1986)
Tetrahedron
1177. Lett.
27
529
264
R.Vanderesse, Lett.
265
M.Lourak,
27 (1986)
Y.Fort
and P.Caubere,
Tetrahedron
5483.
J.Lu and Y.Qian,
Wuji
Huaxue
1 (1985)
130; CA 105
(1986)
190318. 266
Z.Zhang,
X.Liu
and Y.Fan,
30 (1985)
1351;
267
M.Kijima,
Y.Nambu
268
J.O.Osby,
S.W.Heinzman
(1986) 269
270
J.A.Cowan,
271
T.Tsuda,
(1985)
1851.
J.Am.Chem.Soc.
108
H.Toi,
and H.Ogoshi,
943.
Lett.
H.Satomi,
A.-M.Zigna
27 (1986)
1205.
T.Kawamoto
and T.Sageusa,
537.
and G.Balavoine,
J.Organomet.Chem.
306
Y.T.Xian
and G.Balavoine,
J.Organomet.Chem.
306
267. J.G.March
E.Amat,
275
O.A.Karpeiskaya, SSSR, Ser.Khim.
277
Lang.Ed.)
257.
F.Guibe,
T.Tabuchi, (1986)
T.Watanabe,
51 (1986)
274
276
Chem.Lett.
and B.Ganem,
(1986)
T.Hayashi,
F.Guibe,
(1986)
108
Tetrahedron
J.Org.Chem.
273
(Foreign
17047.
and T.Endo,
T.Fujisawa,
Y.Aoyama,
(1986)
(1986)
Tongbao
67.
J.Am.Chem.Soc.
272
CA 105
Kexue
and F.Grases, A.A.Belyi
(1985)
J.Inanaga
J.Mol.Catal.
35 (1986)
and M.E.Vol'pin,
1693; CA 104
(1986)
and M.Yamaguchi,
1.
Izv.Akad.Nauk. 148247.
Tetrahedron
Lett.
27
5237.
M.N.Bakola-Christianopoulou,
J.Organomet.Chem.
308
(1986)
C24. 278
E.Keinan
and N.Greenspoon,
279
A.Karim,
A.Mortreux
(1986) 280
281
and F.Pettit,
108
Tetrahedron
(1986) Lett.
27
K.Ishihara
and H.Yamamoto,
Tetrahedron
Lett.
27
987.
H.Brunner,
R.Becker
and S.Gauder,
Organometallics
739. 282
7314.
345.
A.Mori, (1986)
J.Am.Chem.Soc.
H.Brunner
and M.Kunz,
Chem.Ber.
119
(1986)
2868.
5 (1986)
530 283 284
S.Zehani
and G.Gelbard,
I.Shimizu,
M.Oshima,
J.C.S.Chem.Commun.
M.Nisar
(1985)
and J.Tsuji,
1162.
Chem.Lett.
(1986)
1775. 285
J.Tsuji,
T.Sugiura,
Commun.
(1986)
286
B.T.Khai
287
K.Yanada, (1986)
T.Okano, (1986)
J.Organomet.Chem.
and M.Hirobe,
and H.Alper,
Y.Moriyama,
309 (1986)
Tetrahedron
Lett.
C63.
27
J.Mol.Catal.
H.Konishi
and J.Kiji,
37 (1986)
359.
Chem.Lett.
1463. M.Iwahara
T.Okano, I.Pri-Bar
and T.Suzuki,
and O.Buchman, P.G.Ciattini,
S.Cacchi, Lett.
293
T.Nagano
I.Pri-Bar
289
292
J.C.S.Chem.
5113.
J.Blum,
291
and I.Minami,
922.
and A.Arcelli,
288
290
M.Yuhara
27 (1986)
51 (1986)
J.Org.Chem. E.Morera
(1986)
and G.Ortar,
1467.
734.
Tetrahedron
5541.
K.Tanaka
S.Kuwabata,
Chem.Lett.
and T.Tanaka,
Inorg.Chem.
25 (1986)
1691. 294
Z-Wang,
295
R.Fujiwara
7 (1986)
A.Kirsch-de
119
K.Kasuga,
H.Atarashi,
299
M.Trifan,
V.Marin
A.M.Syroezhko, Uchebn.Zaved., (1986) 301
301
Xuebao
44 (1986)
Y.Rollin
(1986)
and K.Kusuda, (1986)
D.Maetens
(1985)
298
278; CA 105
Huaxue
J.-C.Folest,
225; CA 104
Mesmaeker,
Acta.Chim.Hung.
(1986)
and Q.Zha,
199030.
J.Organomet.Chem.
H.Yamaguchi, Commun.
297
(1986)
S.Pellegrini,
S.Mabrouk, J.Perichon,
296
Z.Deng
C.Li,
863; CA 105
225978.
and R.Nasielski-Hinkens,
Chem.Lett.
(1986)
Makromcl.Chem.,Rapid
245; CA 104
and R.Avram,
and
391.
(1986) 139178.
(1986) 1679. Rev.Chim.(Bucharest)
37
99497.
A.A.Vikhorev,
and A.S.Yakovlev,
Khim.Khim.Tekhnol.
29 (1986)
Izv.Vyssh.
103;
CA 105
96861.
G.Balavoine, H.Rivi&e,
D.H.R.Barton, Tetrahedron
J.Bolvin,
Lett.
27.
A.Gref,
(1986)
2849.
N.Ozbalik
and
531
302
and T.M.Mal'kovskaya,
304
CA 104
A.Nishinaga,
(Decker) 306
307 308
G.Read
and M.Urgelles, (1986)
C.Martin,
M.Faraj,
and P.Dizabo,
309
K.Takehira,
310
V.P.Zagorodnikov,
312
E.Keinan,
Chem.Ind.
129119.
Trans.
J.Mol.Catal.
(1985)
and H.Orita,
M.N.Vargaftik,
(1986)
1591;
63.
J.Mercier,
37 (1986)
201.
Chem.Lett.
D.I.Kochubei,
Izv.Akad.Nauk
(1985)
1835.
A.L.Chuvilin,
SSSR,
Ser.Khim.
160974.
J.C.S.Chem.Commun.
K.K.Seth
37 (1986)
J.-M.Bregault,
J.Mol.Catal.
and M.A.Maifat,
253; CA 104
B.L.Feringa,
and T.Matsuura,
and D.M.M.Rohe, (1986)
J.C.S.Dalton
J.Martin,
T.Hayakawa
311
58 (1985)
5373.
J.Fillaux
(1986)
N.Pingel
and M.Bressan,
S.G.Sakharov
R.Sh.Latipov
Y.Toyoda
T.Shimizu,
309; CA 104
CA 104
A.Morvillo
N.M.Lebedeva,
2257.
W.Brijoux,
22 (1985)
and
108820.
51 (1986)
H.Bbnnemann,
N.Ozbalik
1727.
Zh.Prikl.Khim.(Leningrad)
H.Iwasaki,
J.Org.Chem. 305
(1986)
A.Gref,
(1986)
I.M.Kuznetswa,
R.A.Galimov,
2491;
J.Boivin,
J.C.S.Chem.Commun.
H.Rivibre, 303
D.H.R.Barton,
G.Balavoine,
(1986)
and R.Lamed,
909.
J.Am.Chem.Soc.
108
(1986)
3474. 313
M.Tanaka, (1986)
314
and T.Fuchikami,
K.Januszkiewicz
H.A.Zahalka, (1986)
315
H.Urata
Tetrahedron
Lett.
27
3165. and H.Alper,
J.Mol.Catal.
35
249.
S.Shinoda,
Y.Koie
and Y.Saito,
Bull.Chem.Soc.Jpn.
59 (1986)
2938. 316
W-Adam, (1986)
317
and E.Staab,
Tetrahedron
Lett.
27
2839.
S.E.Creager, (1986)
318
A.Griesbeck
S.A.Raybuck
and R.W.Murray,
J.Am.Chem.Soc.
4225.
I.Tabushi
and M.Kodera,
J.Am.Chem.Soc.
108
(1986)
1101.
108
532
319
M.K.Dickson
P.K.Wong, (1985)
320
I.Tabushi
321
P.J.Martinez Arias
and K.Morimitsu,
J.C.S.Chem.Commun.
(1986)
L.M.Stock,
Tetrahedron
de la Cuesta,
and F.Delgado
CA 105 322
and L.L.Sterna,
1565.
E.Rus
Lett.
Martinez,
27 (1986)
51.
J.M.Blasco
Bayo, An.Quim.,Ser.A
81 (1985)
414;
152354.
and S.H.Wang,
Fuel
64 (1985)
1713;
CA 104
(1986)
53267. 323
G.D.Tkacheva CA 104
324
(1986)
105
- Kochi (1986)
Kogyo
T.P.Kenigsberg,
327
329
28
Koto
Senmon
N.G.Ariko,
and A.Kurokawa, Gakko
23 (1985)
(1985)
(1985)
N.I.Mitskevich
1485;
27; CA 104
1289;
Gakujutsu 111; CA
G.R.Steinmetz
and C.E.Sumner,
CA 105
208316.
129276. Proc.Conf.Coord.Chem.
175255. J.Catal.
Neftekhimiya
F.F.Shcherbina,
5974.
Neftepererab.Neftekhim.
(1986)
(1986)
and V.F.Nazinok,
(1986)
and K.B.Yatsimirskii,
89; CA 104
(1986)
CA 105
and D.N.Tmenov,
Yu.I.Bratushko, 10th
328
T.Kubokawa
26 (1936)
F.V.Shcherbina (Kiev)
21 (1985)
8299.
Kinet.Katal. 326
Zh.Org.Khim.
129590.
M.Shigeyasu,N.Osaki, Kiyo
325
and B.V.Suvorov,
26 (1986)
100
(1986)
549;
409; CA 105 (1986)
225587. 330
A.M.Ivanov CA 104
331
A.M.Ivanov, (1986)
332 333
S.Lundk,
335
and E.V.Shuran,
M.Vaskovh,
34 (1986)
(1985)
N.P.Belous,
1078;
Ukr.Khim.Zh.(Russ.Ed.)
52
133172. J.0rg.Chem.51
P.Lederer
I.V.Zakharov
(1986)
and J.Veprek-Siska,
and P.E.Strizhak,
(1986)
L.K.D'yachek,
(1986)
26 (1985)
1365. J.Mol.
321.
852; CA 104
F.F.Shcherbina, CA 104
(1986)
and H.-C.Szabo,
Yu.V.Geletii, 26
Kinet.Katal.
148087.
372; CA 105
R.DiCosimo
Catal. 334
and E.V.Shuran,
(1986)
N.N.Kalibabchuk,
Ukr.Khim.Zh.(Russ.Ed.) 156515.
Kinet.Katal.
68363. D.N.Tmenov
52 (1986)
100;
and
533 336
A.L.Mosolova CA 105
337
A.B.Goel, 117
25 (1985)
540;
42411.
P.E.Throckmorton
and R.A.Grimm,
Inorg.Chim.Acta
(1986) L15.
338
A.B.Goel,
339
J.van
Inorg.Chim.Acta
Gent,
Bekkum, 340
Neftekhimiya
and A.L.Matienko,
(1986)
S.Hata,
Lett.
S.Ito
(1986) Lll.
A.W.P.G.Peters
A.A.Wismeijer,
Tetrahedron
A.Kunai,
121
27 (1986)
Rit and H.van
1059.
and K.Sasaki,
J.Org.Chem.
51 (1986)
3471. 341
L.Gasella
and L.Rigoni,
342
V.P.Morozov
and T.N.Grishko,
Khim.Tekhnol. 343
K.Nomiya, CA 105
344
(1986)
H.C.Bajaj (1985)
346
1669.
Izv.Vysh.Uchebn.Zaved.,Khim. 31; CA 104
and M.Miwa,
T.Miyazaki
CA 105
(1986)
(1986)
Polyhedron
68352. 5 (1986)
1031;
and M.M.Taqui
and M.Miwa,
Polyhedron
5
69944.
Khan,
339; CA 104 (1986)
M.M.Taqui
(1985)
85754.
Y.Sugie,
(1986) 1267; 345
28 (1985)(5)
H.Murasaki
K.Nomiya,
J.C.S.Chem.Comunun.
React.Kinet.Catal.Lett.
28
148077.
Khan and A.Prakash
Rao, J.Mol.Catal.
35 (1986)
237. 347
M.A.Beckett
and R.B.Homer,
Inorg.Chim.Acta
118
(1986)
Lll. 348
N.N.Tsekhina 59 (1986)
and B.G.Freidlin,
628; CA 105
(1986)
Zh.Prikl.Khim.
(Leningrad)
42115.
349
M.A.Beckett
and R.B.Homer,
Inorg.Chim.Acta
115
(1986) L25.
350
M.A.Beckett
and R.B.Homer,
Inorg.Chim.Acta
122
(1986) L5.
351
V.P.Zagorodnikov
and M.N.Vargaftik,
Ser.Khim.
2652.
352
(1985)
S.Kitagawa, bu Kenkyu
353
M.Munakata Hokoku
N.Kitajima,
354
M.E.Cass
(1985)(21)
K.Whang,
J.C.S.Chem.Commun.
and M.Ohmae,
and C.G.Pierpont,
SSSR,
Kinki
Rikogaku-
83; CA 104
Y.Moro-oka, (1986)
Izv.Akad.Nauk
Daigaku
(1986)
A.Uchida,
224421.
and Y.Sasada,
1504. Inorg.Chem.
25 (1986) 122.
534 355
T.Funabiki,
S.Tada,
T.Yoshioka,
J.C.S.Chem.Commun. 356
357
F.Funabiki,
A.Mizoguchi,
H.Sakamoto
and S.Yoshida,
U.Russo,
M.Vidali,
Inorg.Chim.Acta 358
(1986)
S.Tsuruya,
T.Sugimoto,
and S.Yoshida,
S.Tada,
J.Am.Chem.Soc.
B.Zarli,
120
M.Takano
1699.
R.Furello
M.Tsuji,
108
(1986)
2921.
and G.Maccarrone,
(1986) Lll.
S.-I.Yani
and M.Masai,
Inorg.Chem.
25 (1986)
1072.
141,
536 389
K.Kasuga, CA 105
390
R.B.Homer, (1985)
391
T.Oishi
(1986)
Y.Liu,
R.D.Cannon,
115; CA 104 K.Wang,
Ziran
and Y.Yamamoto,
Polyhedron
5 (1986)
883;
90090.
X.Sun,
Kexueban
S.S.B.Kim,
(1986)
X.Zhu
15 (1985)
392
S.-M.Peng
393
G.Speier
394
E.Balogh-Hergovits
Bull.Korean.Chem.Soc.
and H.Li,
Xibei
(3) 47; CA 104
Inorg.Chim.Acta
and D.-S.Liaw, and L.Parkanyi,
6
50446.
J.Org.Chem.
and G.Speier,
Daxue
(1986)
113
Xuebao,
179064.
(1986)
51 (1986)
J.Mol.Catal.
Lll.
218. 37 (1986)
309. 395
M.M.Al-Arab
and G.A.Hamilton,
J.Am.Chem.Soc.
108 (1986)
5972. 396
I.Ondrejkovicova 10th
397
(1985)
M.M.Taqui
and G.Ondrejovic,
251; CA 104 (1986)
Khan,
Proc.Conf.Coord.Chem.
236144. A.Hussain
M.R.H.Siddiqui,
and M.A.Moiz,
Inorg.Chem.
25 (1986)
398
K.Yamamoto,
Polyhedron
399
D.P.Riley
and J.D.Oliver,
Inorg.Chem.
400
D.P.Riley
and P.E.Correa,
J.C.S.Chem.Commun.
401
A.A.Andreev
403
M.Hronec
(1986)
and L.Malik,
O.Gombosuren, Univ.,Ser.2:
404
5 (1986)
and K.Tashkova,
(4) 59; CA 105 402
2765.
25 (1986)
90148.
1814.
(1986)
Dokl.Bolg.Akad.Nauk
J.Mol.Catal.
26 (1985)
M.A.Ismailova,
Kh.M.Yakubov,
A.N.Astanina,
Zh.Obshch.Khim.
60920.
(1986)
1097.
39 (1986)
63336.
V.V.Berentsveig Khim.
913; CA 105
35 (1986)
169.
and A.P.Rudenko, 588; CA 104
E.Ya.Offengenden 56 (1986)
Vest.Mosk.
(1986)
40544.
and
527; CA 105
(1986)
537 407
R.Rajaram
K.Vijayasri, 117
(1986)
Huaxue
Xuebao
408
W.Chen,
409
J.Muzart,Tetrahedron
410
J.P.Collman, 108
411
(1986)
(1986) 413
414
416
A.Kunai,
(1986)
418
S.Hata,
420
421
CA 104
S.Ito
and K.Sasaki,
108
J.Mol.Catal.
36
J.Am.Chem.Soc.
108
and S.M.Hecht,
J.Am.Chem.
7839. Chem.Soc.
V.M.Derkacheva,
(1986)
6 (1985)
I.A.Zheltukhin,
and E.A.Luk'yanets,
(3) 138;
O.L.Kaliya,
Zh.Org.Chim.
21 (1985)
185790.
C.D.Stucky
and C.A.Tolman,
E.A.Wahab,
Egypt.J.Chem.
J.C.S.Chem.Commun.
27 (1984) 81; CA 104
E.Kotani,
S.Kobayashi,
33 (1985)
H.Orita,
4680;
T.Hayakawa
Y.Ishii CA 105
and S.Tobinaga, (1986)
and K.Takehira,
Chem.Pharm.
78558. Bull.Chem.Soc.Jpn.
59
2637.
Y.Sasson,
S.C.Pati,
G.D.Zappi
and R.Neumann,
H.P.Pathy
and B.R.Dev,
J.Org.Chem.
51 (1986)
~ Proc.Indian
Part A 51 (1985) 853; CA 105 (1986) 423
J.Am.Chem.Soc.
185801.
2880. 422
J.C.S.
1521.
I.Ahmed,
(1986)
and D.Mansuy,
and J.K.Kochi,
R.L.Mutholland,
(1986)
N.Herron,
Bull.
J.Am.Chem.Soc.
6012.
S.V.Barkanova,
(1986) 419
J.F.Bartoli
J.Suh and K.Nahm, Bull.Korean CA 104 (1986) 129277.
(1986)
3139.
and K.S.Suslick,
S.Perrier
V.N.Kopranenkov
417
5968.
341.
T.J.Reinert
D.C.Heimbrook,
2018;
(1986)
297.
Sot. 108 415
27 (1986)
and J.I.Braumann,
J.-P.Renaud,
K.Srinivasan,
(1986)
Lett.
891; CA 105
7281.
(1986) 413a
43 (1985)
T.Kodadek
P.Battioni,
B.R.Cook,
Inorg.Chim.Acta
2588.
Chem.Commun. 412
and J.C.Kuriacose,
133.
N.I.Kuznetsova, Yu.I.Yermakov,
M.A.Fedotov, J.Mol.Catal.
Natl.Sci.Acad.,
152387.
V.A.Likholobov 38 (1986)
263.
and
538 424
S.Yamaguchi, (1986)
425
S.Yamaguchi, (1986)
426
and S.Enomoto,
Bull.Chem.Soc.Jpn.
M.Inoue
and S.Enomoto,
Chem.Pharm.Bull.
445; CA 105 (1986)
L.A.Deardurff, 51 (1986)
427
M.Inoue
59
2881. 34
208291.
M.S.Alnajjar
and D.M.Camaioni,
J.Org.Chem.
3686.
A.L.J.Beckwith
and A.A.Zavistas,
J.Am.Chem.Soc.
108
(1986)
8230. 428
E.V.Dehmlov CA 104
429
and J.K.Makrandi,
(1986)
J.M.Klunder, (1986)
J.Chem.Res.Synop.
(1986)
32;
185804. S.Y.Ko
and K.B.Sharpless,
J.Org.Chem.
51
3710.
430
R.M.Hanson
and K.B.Sharpless,
J.Org.Chem.
51 (1986)
1922.
431
J.G.Millar
and E.W.Underhill,
J.Org.Chem.
51 (1986)
4726.
432
H.J.Gordon, Synth.
433
Y.Kitano, Commun.
434
K.B.Sharpless,
63 (1985)
T.Matsumoto, (1986)
C.Puchot,
O.Samuel,
S.Hatakayama, (1985)
R.E.Babine,
437
M.Kawai,
440
K.Sakurai
S.Zhao,
Lett.
C.Agami
and H.B.Kagan,
J.C.S.Chem.Commun.
27 (1986)
and D.H.Rich,
R.Lazaro, Lett.
Y.Honda,
A.Ori,
R.Barret,
5791.
Tetrahedron
Lett.
27
H.Ranieriseheno
and P.Viallefont,
27 (1986) 4735.
and G.Tsuchihashi,
F.Pautet,
M.Daudon
Chem.Lett.
and B.Mathian,
(1986)
1417.
Bull.Soc.Chim,
94 (1985) 439; CA 104 (1986) 88158.
P.Mosset,
(1985)
J.C.S.Chem.
2353.
and S.Takano,
Tetrahedron
Tetrahedron
W.Xiao,
and F.Sato,
1877.
Tetrahedron 442
(1986)
R.Jacquier,
Belg. 441
E.Dunach,
108
J.H.Gardner
(1986)
439
Org.
1759.
436
438
Y.Takeda
and R.Regenye, 88368.
1732.
J.Am.Chem.Soc. 435
C.M.Exon
66; CA 104 (1968)
P.Yadagiri, Lett.
Y.Gong,
S.Lumin,
27 (1986)
C.Feng,
364; CA 105
Z.Wang
(1986)
J.Capdevilla
and J.R.Falck,
6035. and W.Xu,
133147.
Cuihua
Xuebao
6
539 443
444
P.J.Martinez
Minguez,
181; CA 104
(1986) 7460.
P.J.Martinez Medina, (1986)
445
X.Ye,
S.Qu
Aceites
Aceites
and
(Seville)
E.Rus Martinez
(Seville)
36 (1985)
and A.Justicia
36 (1985)
177; CA 104
and Y.Wu,
Huaxue
Xuebao
43 (1985)
572; CA 104
19254.
Y.Kurusu, (1986)
447
de la Cuesta,
Grasas
E.Rus Martinez
Grasas
7459.
(1986) 446
de la Cuesta,
L.M.Cotoruelo
Y.Masuyama,
M.Saito
and S.Saito,
J.Mol.Catal.
37
235.
J.Prandi,
H.B.Kagan
(1986)
2617.
448
D.Prat
and R.Lett,
449
D.Prat,
B.Delpech
and H.Mimoun,
Tetrahedron and R.Lett,
Tetrahedron
Lett.
Lett.
27 (1986)
Tetrahedron
27
707.
Lett.
27 (1986)
711. 450
C.L.Hill
and R.B.Brown,
451
R.J.M.Nolte, Sot. 108
452
B.De
453
J.A.S.J.Razenberg,
S.Takagi, (1986)
455
and B.Meunier,
(1986)
(1986)
and R.Schuurman,
536. J.Am.Chem.
J.C.S.Perkin
Trans.11.
(1985)
42569. R.J.M.Nolte
and W.Drenth,
J.C.S.Chem.
277.
T.K.Miyamoto
and Y.Sasaki,
Bull.Chem.Soc.Jpn.
59
2371.
K.Srinivasan, (1986)
108
2751.
CA 104 (1986)
Commun. 454
J.A.S.J.Ranzenberg
(1986)
Poorter
1735;
J.Am.Chem.Soc.
P.Michaud
and J.K.Kochi,
J.Am.Chem.Soc.
108
2309.
456
C.-M.Che,
457
Y.Tatsuno,
W.-K.Cheng, A.Sekiya,
J.C.S.Chem.Commun. K.Tani
and T.Saito,
(1986)
1443.
Chem.Lett
(1986)
889. 458
T.C.Woon, (1986)
459
460
L.Devocelle,
9 (1985)
J.P.Collman, 108
and T.C.Bruice,
J.Am.Chem.Soc.
108
7990.
D.Mansuy, Chim.
C.M.Dicken
(1986)
I.Artaud
711; CA 104
P.D.Hampton 7861.
and J.P.Battioni,
(1986)
Nouv.J.
144570.
and J.I.Brauman,
J.Am.Chem.Soc.
461
T.C.Woon
C.M.Dicken, (1986)
and T.C.Bruice,
J.Am.Chem.Soc.
108
1636.
462
J.T.Croves
463
S.Takagi,
and Y.Watanabe, E.Takahashi
J.Am.Chem.Soc.
and T.K.Miyamoto,
108
(1986)
Chem.Lett.
507.
(1986)
1275. 464
T.G.Traylor, D.Dolphin,
465
108
Y.Iamamoto
P.S.Traylor
(1986)
and
2783.
and T.Nakano,
J.Am.Chem.Soc.
108
3529. J.Umehara,
T.Muto,
F.C.Bradley
B.P.Murch,
T.Miura
H.Masumori,
33 (1985) 4749;
Pharm.Bull. 467
B.E.Dunlap,
J.Am.Chem.Soc.
T.G.Traylor, (1986)
466
T.Nakano,
CA 105
and L.Que,
and M.Kimura,
(1986)
Chem.
134234.
J.Am.Chem.Soc.
108
(1986)
5027. 468
A.Kittaka,
Y.Sugano, H.Umezawa,
469
M.Otsuka,
Tetrahedron
J.C.DObsOn,
W.K.Seok
Lett.
M.Ohno,
Y.Sugiura
27 (1986)
and T.J.Meyer,
and
3635.
Inorg.Chem.
25 (1986)
1513. 470
C.-M.Che
and W.C.Chung,
471
C.M.Che,
W.K.Cheng
J.C.S.Chem.Commun.
and T.C.W.Mak,
(1986)
386.
J.C.S.Chem.Commun.
(1986)
200. 472
A.F.Tai, 108
473
L.D.Margerum
(1986)
V.I.Korenskii, V.L.Volkov, Khim.
474
475
V.D.Skobeleva,
G.S.Zakharova
55 (1985)
1969;
J.R.L.Smith,
D.I.Richards, Trans.
O.Bortolini,
V.Conte,
(1986)
C.B.Thomas
II (1985) F.Di
I.P.Kolenko, Zh.Obshch.
87965. and W.Whittacker,
1677; CA 104
Furia
L.G.Shevchuk,
and V.G.Kul'nevich,
477
V.G.Kharchuk,
(1986)
and C.Modena,
108i308.
J.Org.Chem.
2661.
S.P.Gavrilova,
(1986)
J.Am.Chem.Soc.
and V.N.Vinogradova,
CA 104
J.C.S.Perkin
51 (1986) 476
and J.S.Valentine,
5006.
L.A.Badovskaya,
Kinet.Catal.
26 (1985)
N.A.Vysotskaya 1248; CA 104
50460.
C.Venturello
and M.Ricci,
J.Org.Chem.
51 (1986)
1599.
541
478
479
M.Lj.Mihailovic, Tetrahedron
Lett.
M.B.Booking
and D.J.Intihar,
Chem.Technol. 480
N.Goto Kiyo,
481
35A
485
486
(1986)
488
Koto
Senmon
57; CA 105 (1986)
A.Kajiwara
H.Tomioka,
59 (1986)
J.Jagannadham,
Gakko
42406.
J.Am.Chem.Soc.
a (1985)
108
and H.Nozaki,
B.Sethuram
41; CA 105
J.Rajaram
Bull.Chem.
and N.T.Rao,
(1986)
Curr.Sci.
54
133378.
and K.S.Tripathy, 1; CA 104 (1986)
E.J.Smith,
Oxid.
208277.
and J.C.Kuriacose,
(1986)
P.S.Radhakrishnamurti
Trans.
J.C.S.
105.
1279; CA 105
J.A.Cabeza,
and A.Nakamura,
K.Oshima
M.A.Rao,
K.Vijayashri,
Dalton
Kogyo
96830.
434.
Sci., Sect A 5 (1985) 487
Niihama
and T.C.Bruice,
T.Sugawara,
S.Kanemoto,
(1985)
J.Chem.Technol.Biotechnol.,
365; CA 105 (1986)
5495.
N.Ueyama,
Commun.
and R.Vukicevic,
2287.
21 (1985)
P.N.Balasubramanian
Soc.Jpn. 484
(1985)
and M.Kidawara,
Chem.Commun. 483
27 (1986)
Rikogaku-hen
(1986) 482
S.Konstantinovic
H.Adams
Indian
J.Phys.Nat.
87950.
and P.M.Maitlis,
J.C.S.
(1986) 1155.
H.Hingorani,
H.C.Goyal,
Rev.Roum.Chim.
G.Chandra
30 (1985)
489
R.B.Ganunill and S.A.Nash,
490
S.J.Danishefsky
and S.N.Shrivastava,
725; CA 104 (1986) J.Org.Chem.
and M.P.DeNinno,
148081.
51 (1986)
3116.
J.Org.Chem.
51 (1986)
Tetrahedron
41 (1985)
2615. 491
492
H.Nagashima,
K.Sato
and J.Tsuji,
5645: CA 105
(1986)
171451.
B.M.Choudary
and M.Lakshmi
Kantam,
J.Mol.Catal.
36 (1986)
343. 493
S.C.Goyal
and L.K.Saxena,
554; CA 104 494
P.Smith (1986)
(1986)
and K.R.Maples, 152435.
J.Indian
Chem.Soc.
62 (1985)
185802. J.Magn.Reson.
65 (1985)
491; CA 105
495
R.Barret, (1985)
496
728; CA 104 (1986;
D.G.Batyr,
497
Mold.SSSR,
(1986)
D.G.Batyr,
498
B.Pispisa CA 104
499
(1985) 500
!1985)
(5) 52;
and Yu.Ya.Kharitonov,
435; CA 105 (1986)
78338.
Macromolecules
19 (1986)
S.Hansson
E.Amat
and C.Moberg,
(1986)
Acta
and J.G.March,
Bull.Soc.Chim.Fr.
501
K.Nakamija,
M.Kojima
and J.Fujita,
Chem.Lett.
502
E.W.Harlan,
J.M.Berg
and R.H.Holm,
J.Am.Chem.Soc.
504
O.Bortolini,
505
W.Ando
506
T.Takata
508
1483.
108
108
Lett.
Tetrahedron T.Takata
27 (1986)
Lett.
27 (1986)
and S.Oae,
3391. 1591.
Tetrahedron
581.
C.Frechou
and G.Demailly,
Tetrahedron
Lett.
2867.
P.Ferraboschi,
M.N.Azadani
and E.Santaniello,
43; CA 105 (1986)
510
H.Kang
and J.L.Beauchamp,
511
P.S.R.Murti,
H.P.Panda
227; CA 105
J.W.Suggs
and M.Rossi,
6257.
Tetrahedron
S.Fujiwara,
27 (1986)
16 (1986)
512
(1986)
J.Am.Chem.Soc.
G.Modena
G.Licini,
27 (1986)
and W.Ando,
G.Solladie,
(1985)
and R.H.Holm,
F.Di Furia,
and L.Huang,
27 (1986) 509
E.W.Harlan
Lett.
K.Fujimori, Lett.
42083.
7856.
Tetrahedron
507
(1985)
6992.
J.P.Caradonna, (1986)
B39
185949.
(1986)
503
904;
Chem.Scand.
594; CA 105
(1986)
Izv.
130236.
593; CA 104
F.Grases,
and S.V.Kil'mininov,
A.A.Kirienko
and A.Palleschi,
T.Antonsson,
40
129324.
Ser.Biol.Khim.Nauk
12 (1986)
(1986)
Pharmazie
75886.
V.G.Isak,
Koord.Khim.
and M.Daudon,
A.A.Kirienko
V.G.Isak,
Akad.Nauk CA 104
B.Mathian
F.Pautet,
and L.Ytuarte,
J.Am.Chem.Soc.
and D.C.Pradhan,
(1986)
Synth.Commun.
152219. 108
(1986)
Oxid.Commun.
5663. 8
208296. Tetrahedron
Lett.
27 (1986)
437.
543
513
B.Bhattacharjee, M.N.Bhattacharjee, M.Bhattacharjee and A.K.Bhattacharjee, Bull.Chem.Soc.Jpn. 59 (1986) 3217.
514
515
R.Gulge, and A.M.Shaligram, Indian J.Chem. 24B (1985) 815; CA 105 (1986) 172757. F.P.Ballistreri, S.Failla, G.A.Tomaselli and R.Curci, Tetrahedron Lett. 27 i1986) 5139.
516
F.Freeman and J.C.Kappos, J.Org.Chem. 51 (1986) 1654.
517
I.H.Al-Wahaib, B.S.Razouki and B.S.Abdul-Aziz, J.Pet.Res. 5 (1986) 55; CA 105 (1986) 193297.
518
P.Viski, Z.Szeverenyi and L.Simdndi, J.Org.Chem. 51 (1986) 3213.
519
P.Guiton, S.Menager and O.Lafont, Ann.Pharm.Fr. 43 (1985) 373; CA 105 (1986) 5998.
520 521
T.Ogino, T.Kazama and T.Kobayashi, Chem.Lett. (1985) 1863. J.F.Perez-Benito and D.G.Lee, Can.J.Chem. 63 (1985) 3545; CA 104 (1986) 19269.
522
D.G.Lee, K.C.Brown and H.Karaman, Can.J.Chem. 64 (1986) 1054; CA 105 (1986) 190337.
523
R.Rathore, P.S.Vankar and S.Chandrasekaran, Tetrahedron Lett. 27 (1986) 4079.
524
Y.Landais, A.Lebrun and J.P.Robin, Tetrahedron Lett. 27 (1986) 5377.
525
Y.Landais and J.-P.Robin, Tetrahedron Lett. 27 (1986) 1785.
526
E.Vedejs and C.M.McClure, J.Am.Chem.Soc. 108 (1986) 1094.
527
M.Tokles and J.K.Snyder, Tetrahedron Lett. 27 (1986) 3951.
528
T.Yamada and K.Narasaka, Chem.Lett. (1986) 131.
529
J.E.Rice, E.J.LaVoie, D.J.McCaustland, D.L.Fischer and J.C.Wiley, J.Org.Chem. 51 (1986) 2428.
530
Z.Cvengrosovh, M.Hronec, J.Kizlink, T.Pasternakova, S.Holotik and J.Ilavsky, J.Mol.Catal. 37 (1986) 349.
531
E.Baciocchi, A.Dalla Cort, L.Eberson, L.Mandolini and C.Rol, J.Org.Chem. 51 (1986) 4544.
532
T.Morimoto, M.Hirano and T.Koyama, J.C.S.Ferkin Trans.11 (1985) 1109; CA 104 (1986) 50452.
544 533
I.V.Kozhevnikov,
534
D.Dimitrov, (1984)
535
V.I.Kim,
Ser.Khim.
SSSR,
(1985)
V.Sirakova
399; CA 104
E.V.Gusevskaya,
536
(1986)
Izv.Akad.Nauk
(1986)
and R.Stefanova,
224419.
Oxid.Conunun.
7
88854.
I.E.Beck,
A.G.Stepanov,
Yu.I.Yermakov
V.M.Nekipelov, 37 (1986)
and E.P.Talzi,
2167; CA 104
V.A.Likholobov,
and K.I.Zamaraev,
J.Mol.Catal.
177.
J.-E.Backvall
and A.Heumann,
J.Am.Chem.Soc.
108
(1986)
7107. 537
J.Skarzewski
and J.Mlochowski,
963; CA 105 538
539
F.Casablanca,
Chim.Acta
113
H.Mimoun,
M.Mignard,
108
542
G.Amato,
A.Arcoria,
J.Mol.Catal.
37 (1986)
545
F.Di
35 (1986)
(1986) 546
547
548
Furia,
G.A.Tomaselli, and G.Valle,
F.Di
Furia
and
2374.
G.Modena
S.S.Gupta
1503; CA 104
J.C.S.Perkin
and G.A.Ayoko,
(1986)
M.P.Alvarez CA 105
129189.
and A.Schionato,
J.Mol.
and A.Banerjee,
J.C.S.Perkin
(1986) 87964. N.Chandrasekara,
K.Ramalingam
Trans.
1183; CA 104
II (1985)
5374.
M.A.Olatunji CA 105
and Y.Kita,
(1986)
G.Modena
G.A.Tomaselli,
51 (1986)
J.G.Lakshmanan,
and K.Selvaraj,
J.Am.Chem.
47.
S.Dey,
II (1985)
P.G.Arjunan,
Inorg.
165.
F.P.Ballisteri,
K.K.S.Gupta, Trans.
F.Di Furia,
J.Org.Chem.
O.Bortoloni,
Y.Tamura
2743; CA 104
F.P.Ballistreri,
V.Conte,
A.Arcoria,
and J.Fischer,
and L.Saussine,
M.Sakamoto,
33 (1985)
O.Bortolini,
Catal. 544
P.Brechot
T.Kawasaki,
G.Modena, 543
Y.Gauffreteau
3711.
Chem.Pharm.Bull. 541
(1985)
(1986) 173.
(1986)
C.S.Chien,
327
171921.
M.Postel,
Sot. 540
(1986)
J.Prakt.Chem.
Macho,
(1986)
V.Jagannadham, 8 (1985)
Bull.Soc.Chim.Fr.
(1985)
705;
22 (1985)
499;
171597. Acta Cient.Compostelana
23797. M.A.Rao,
31; CA 105
B.Sethuram
(1986)
96837.
and T.N.Rao,
Oxid.Commun.
545
549
M.Mazumdar,
G.Mishra, (India)
S.K.Laha
57 (1985) 187; CA 105
550
N.F.Magri
551
T.Brunelet,
and D.G.I.Kingston, C.Jouitteau
and R.Prasad, (1986)
J.Inst.Chem.
208432.
J.Org.Chem.
and G.Gelbard,
51 (1986)
J.Org.Chem.
797. 51
(1986) 4016. 552
553
15 (1985)
T.Brunelet CA 104 S.Kim
555
S.Czernecki,
557
559
R.Varadarajan
and R.K.Dhar, 153419.
(1986)
S.A.Vorskanyan,
M.S.Akhtar,
J.Org.Chem.
51
J.M.Antelo,
and H.Kim, F.Arce,
Chim.Ital.
115
R.Gurumurthy (1986)
1; CA 104
and M.Copalakrishnan,
565
R.W.Curley
566
A.Abiko,
(1986)
R.Bartzatt
474;
Arm.Khim
J.Heterocycl.Chem.
22
Lett.
27 (1986)
4889.
and A.Varela,
(1986)
Gazz.
129294.
Indian
J.Chem.
25A
208305. Bull.Assoc.Kinet.India
7(2)(1985)
14104.
and C.J.Ticoras, J.C.Roberts,
Lett.
(1986)
133680.
J.Franco
493; CA 104
and D.N.Shanna,
25A
and Sh.O.Badanyan,
Tetrahedron
(1986)
J.Chem.
152638.
A.Castro,
(1985)
476; CA 105
R.Simlot
Indian
(1986)
(1986)
and H.Christol,
1775.
and A.P.Bhaduri,
1323; CA 105
562
P.Morand
Zh.A.Chobanyan 424; CA 105
M.Seth
M.F.Schlecht
567
3297.
186768.
and G.Ville,
27 (1986)
CA 105
hedron
264;
and K.Vijayakumaran,
11; CA 104 (1986)
E.Torreilles, Lett.
561
564
59 (1986)
C.L.Stevens
K.Vijayakumaran
H.-J.Cristau,
(1985)
563
Bull.Chem.Soc.Jpn.
16 (1986)
Zh. 38 (1985) 560
(1985)
5472.
Tetrahedron 558
J.Chem.Res.,Synop.
C.Georgoulis,
Synth.Commun.
(1986)
Synth.
133714.
50453.
and D.C.Lhim,
S.Czernecki,
and C.Palomo,
1197; CA 105 (1986)
and G.Gelbard,
(1986)
554
556
F.P.Cossio
A.Gonzales,
C.Lopez, Commun.
27 (1986)
and J.Carr,
J.Org.Chem.
T.Takemasa
51 (1986)
and S.Masamune,
256. Tetra-
4537. Transition
Met.Chem.
11 (1986)
414.
568
569
K.S.Kim, 27 (1986)
2875.
Manibala,
P.K.Tandon
266 570
N.H.Lee
Y.H.Sonq,
(1985)
and B.Krishna,
1153; CA 104
M.E.Marmion
and C.S.Hahn,
Tetrahedron
Lett.
Z.Phys.Chem.(Leipziq)
(1986) 75900.
and K.J.Takeuchi,
J.Am.Chem.Soc.
108
(1986)
510. 571
L.Roecker
572
P.Kumar, 29
573
K.C.Gupta
(1985)
575 576
577
Bull.
579
CA 105 (1986)
2053.
(1986)
Zh.
80922.
J.C.S.Dalton
434; CA 105
(2) 92; CA 105
Trans.
105
and P.K.Tandon, (1986)
(1986)
(1986)
Orient.J.Chem.
208322,
and G.S.S.Murthy,
(1986)
J.Indian
96827.
and G.S.S.Murthy,
V.J.Jaqannadham
J.S.Thompson
87938.
and V.I.Kurlyankina,
B.Krishna
V.Jaqannadham
255; CA
(1986)
1145; CA 105
H.S.Sinqh,
T.R.Reddy,
607;
179144.
62 (1985)
8 (1985) 581
A.I.Buyanov
and D.H.Macartney,
T.R.Reddy,
26 (1985)
Natl.Acad.Sci.Lett.
59 (1986)
J.W.Herbert
2 (1986) 580
(4) 111; CA 104
56 (1986)
Chem.Soc.
React.Kinet.Catal.Lett.
and A.P.Sinqh,
Chem.Soc.Jpn.
L.G.Revel'skaya,
M.Manibala,
4066.
136716.
Kinet.Katal.
Obshch.Khim.
1931; 578
8 (1985)
M.Kohno,
108 (1986)
33701.
A.K.Singh
(India)
(1986)
and B.Krishna,
(1986)
B.Singh,
J.Am.Chem.Soc.
and K.Vehari,
297; CA 104
P.K.Tandon CA 104
574
and T.J.Meyer,
Oxid.Commun.
208298.
and J.C.Calabrese,
J.Am.Chem.Soc.
108
(1986)
1903. 582
J.Dzigiec,
583
N.K.Mohanty
Pol.J.Chem.
59 (1985) 731; CA 105
and R.K.Nanda,
Bull.Chem.Soc.Jpn.
(1986)
190329.
58 (1985)
3597. 584
H.Laatsch,
Liebigs
Ann.Chem.
(1986)
1655; CA 105
(1986)
225989. 585
M.Varma CA 104
and K.C.Nand, (1986)
51031.
React.Kinet.Catal.Lett.
27 (1985)
97;
547
586
R.D.Kharga and H.B.Mishra, J.Nepal.Chem.Soc. (1983) (3) 45; CA 104 (1986) 50448.
587
M.Uma and A.Manimekalai, Indian J.Chem.,Sect.B. 24B (1985) 1088; CA 105 (1986) 23800.
588
J.-M.Melot, F.Texier-Boullet
and A.Foucaud, Tetrahedron
Lett. 27 (1986) 493. 589
C.S.Chien,
T.Takanami, T.Kawasaki and M.Sakamoto, Chem.
Pharm.Bull. 33 (1985) 1843; CA 104 (1986) 109407. 590
P.V.Sreenivasulu, M.Adinarayana, B.Sethuram and T.N.Rao, Oxid.Ccmunun. 8 (1985) 199; CA 105 (1986) 190262.
591
R.Iqbal and F.Malik, J.Chem.Soc.Pak. 8 (1986) 83; CA 105 (1986) 226295.
592
F.Mata-Perez and J.Perez-Benito, Acta Cient.Compostelana 22 (1985) 563; CA 104 (1986) 224422.
593
F.Mata-Perez and J.Perez-Benito, Z.Phys.Chem. Leipzig (1986) 120; CA (1986) 136609.
594
M.A.El-Dessouky and N.M.El-Mallah, Bull.Soc.Chim.Fr.
267
(1985)
163; CA 104 (1986) 19249. 595
P.V.S.Rao, G.V.Saradamba and K.Ramakrishna, Indian J.Chem. 24A (1986) 438; CA 104 (1986) 185781.
596
N.Nath and L.P.Singh, Rev.Roum.Khim. 31 (1986) 489; CA 105 (1986) 85792.
597
A.A.Awashti and S.K.Upadhyay, Indian J.Chem. 25A (1986) 292; CA 105 (1986) 5868.
598
J.W.Bunting and D.Stefanidis, J.Org.Chem. 51 (1986) 2060.
599
J.W.Bunting and D.Stefanidis, J.Org.Chem. 51 (1986) 2068.
600
S.Yoshifuji, Y.Arakawa and Y.Nitta, Chem.Pharm.Bull. 33 (1985) 5042; CA 105 (1986) 190876.
601
S.Yoshifuji, K.Tanaka, T.Kawai and Y.Nitta, Chem.Pharm. Bull. 33 (1985) 5515; CA 105 (1986) 97895.
602
N.Tangari, M.Giovine, F.Morlacchi and C.Vetuschi, Gazz. Chim.Ital. 115 (1985) 325; CA 104 (1986) 50776.
603
N.G.Gerleman, L.V.Krasnyi-Admoni, Yu.B.Yakovlev and G.A. Shagisultanova, Kinet.Katal. 26 (1985) 1085; CA 104 (1986) 167821.
548 604
K.Hegetschweiler
605
M.Ignaczak 4 (1985)
and S.Komisarski, 47; CA 104 (1986)
606
W.Aadam
607
R.Gamboniand
608
and P.Saltman,
and B.B.Lohray,
K.Nytko
C.Tamm,
609
F.Freeman
and L.Y.Chang,
610
F.Grases,
J.Palou
(1986) 611
612
107.
Chim.
98 (1986)
Lett.
185.
27 (1986)
3999.
Zesz.Nauk.Polytech.Bialostockiej: 113;CA
105 (1986)
J.Am.Chem.Soc.
and E.Amat,
34890.
108
Transition
(1986)
4504.
Met.Chem.
11
253.
D.Laloo (1986)
Acta Univ.Lodz.,Folia
Tetrahedron
9 (1985)
25 (1986)
148073.
Angew.Chem.
and H.Sobolewska,
Mat.Fiz.,Chem.
Inorg.Chem.
and M.K.Mahanti,
Afinidad
42 (1985)
593; CA 105
23796.
R.L.Bartzatt
and J.Carr,
Transition
Met.Chem.
11 (1986)
116. 613
614
J.Riefkohl,
L.Rodriguez,
J.Org.Chem.
51 (1986)
T.Ya.Volkova, Mokslu
615
G.I.Rozovskii
Akad.Darb.,Ser.B
H.K.Baek, (1986)
K.D.Karlin
G.Sampoli
and F.A.Souto,
and A.A.Sakharov,
(1985)
(2) 3; CA 104
and R.A.Holwerda,
Liet.TSR (1986)
Inorg.Chem.
206679. 25
2347.
616
I.Kawafune,
617
S.Miyano,
Chem.Lett. H.Fukushima,
Chem.Soc.Jpn. 618
L.Romero,
2468.
H.K.Lee, CA 105
B.H.Chang
T.Matsue,
620
J.T.Groves
621
S.Torii,
1503.
H.Inagawa
and H.Hashimoto,
Bull.
59 (1986) 3285.
(1986)
619
(1986)
and H.R.Kim,
Pollimo
9 (1985)
97102;
97102.
T.Kato,
U.Akiba
and J.A.Gilbert, T.Inokuchi
and T.Osa,
Chem.Lett.
Inorg.Chem.
and T.Sogiura,
(1986)
25 (1986)
J.Org.Chem.
123.
51 (1986)
155. 622
W.Kutner, R.W.Murray, 205
(1986)
J.A.Gilbert,
A.Tomaszewski,
T.J.Meyer
J.Electroanal.Chem.Interfacial 185; CA 105
(1986)
122768.
843.
and
Electrochem.
549
623
R.A.Reed
and R.W.Murray, 200
Electrochem. 624
K.Araki
J.Electroanal.Chem.Interfacial
(1986) 401; CA 105
and S.Shiraishi,
(1986)
14059.
Bull.Chem.Soc.Jpn.
59 (1986)
229. 625
M.E.Fakley,
Organomet.Chem.
14 (1986)
373; CA 105
(1986)
96671. 626
B.V.Romanovskii,
Acta
Phys.Chem.
31 (1985)
215; CA 104
(1986) 11038. 627
K.H.Schmidt,
Chem.Ind.(Diisseldorf)
37 (1985) 762: CA 104
(1986) 111735. 628
Crit.Rep.Appl.Chem.
R.Whyman,
12 (1985)
128; CA 104
(1986)
136669. 629
J.J.Zidlkowski, CA 104
630
(1986)
G.W.Parshall CA 104
631
Prof.Conf.Coord.Chem.lOth
and R.E.Putscher,
(1986)
R.L.Pruett,
(1985)
519;
175210. J.Chem.Educ.
63 (1986)
189;
185542.
J.Chem.Educ.
63 (1986)
196; CA 104
(1986)
188594. 632
I.Ojima
and K.Hirai,
104 (1986) 633 634
I.Ojima,
J.Mol.Catal.
37 (1986)
5 (1985)
102; CA
25,
A.A.Kelkar,
R.M.Deshpande,
[Proc.Natl.Symp.Catal.\,
S.B.Dake
and R.V.Chaudhari, 7th
(1985)
43; CA 105
60267.
B.Juran (1986)
636
Synth.
Adv.Catal., (1986) 635
Asymmetric
147885.
and R.V.Porcelli, (10, Sect.1)
B.D.Dombek,
Hydrocarbon
85; CA 104
Process.,
Int.Ed.
(1986) 70655.
J.Chem.Educ.
63 (1986)
210; CA 104 (1986)
Wiad.Chem.
39 (1985)
667; CA 105
188596. 637
A.F.Borowski,
(1986)
210722. 638
H.Des
Abbayes,
Isr.J.Chem.
26 (1985)
249; CA 104
(1986)
231265. J.Organomet.Chem.
639
H.Alper,
640
Yu.N.Kukushkin, 140857.
Hoord.Khim.
300
(1986)
12 (1986)
1. 147; CA 104
(1986)
64
550 641
S.Inoue
and H.Koinuma,
CA 105 642
(1986)
D.Mahajan
B.James,
Transition", 643
1st
R.Kh.Freidlina, Chukovskaya,
Rev.Inorg.Chem.
6 (1984)
291;
30703. and C.G.Young, (1985)
R.G.Gasanov,
Usp.Khim.
Simp.Quim.Inorg.“Met.
32; CA 104
24789.
(1986)
N.A.Kuz'mina
54 (1985)
and E.Ts.
1127; CA 104
(1986)
148933. 644
M.Huang,
C.Ren,
Y.Jiang,
Organosilicon
Y.Zhou,
Symp.Organosilicon (1986) 645
646
X.Cao,
D.Dong,
Bioorganosilicon
L.Zhao,
Chem.,
Chem.]
7th 1984,
(1985)
Y.Liu
and
!Proc.Int.
275; CA 104
148942.
Yu.I.Yermakov
and L.N.Arzamaskova,
27 (1986)
459; CA 105 (1986)
J.Halpern,
Chem.Ind.(Dekker)
Stud.Surf.Sci.Catal.
232995. 22 (1985)
3; CA 104 (1986)
50455. 647
J.Halpern,
Asymmetric
Synth.5
(1985)
41; CA 104 (1986)
185627. 648
K.E.Koenig,
Asymmetric
Synth.
5 (1985)
71; CA 104 (1986)
185628. 649
H.Brunner,
J.Organomet.Chem.
300 (1986)
650
H.B.Kagan,
Asymmetric
5 (1985)
Synth.
39.
1; CA 104
(1986)
222; CA 104
(1986)
167664. 651
W.S.Knowles,
J.Chem.Educ.
63 (1986)
207621. 652
P.Caubere,
Pure.Appl.Chem.
57 (1985)
1875;
CA 105
(1986)
97057. 653
S.K.Srinivasan, Adv.Catal., CA 104
654
(1986) 655 656
(1986)
M.Troupel,
S.Narasimhan
and N.Venkatasubramanian,
[Proc.-Natl.Symp.Catal.1,
7th
(1985)
315;
186057.
Ann.Chim.(Rome)
76 (1986)
(5-6) 151; CA 105
160667.
E.Steckhan,
Angew.Chem.
D.Schnurpfeil, Leuna-Merseburg
98 (1986)
681.
Wiss.Z.Tech.Hochsch."Carl 27 (1985)
282; CA 105
Schorlemmer" (1986)
78449.
551
657
I.P.Skibida,
Usp.Khim.
658
T.Mlodnicka,
J.Mol.Catal.
659
B.Meunier,
54 (1985)
1487;
36 (1986)
Bull.Soc.Chim.Fr.(l986)
CA 104
(1986)
50405.
205, 578; CA 105 (1986)
171443. 660
V.N.Sapunov,
N.N.Lebedev,
Int.Congr.Catal.8th 661
K.B.Sharpless,
I.Yu.Litvintsev
5 (1984) V359;
and V.D.Vardanyan,
CA 105
(1986)
Chem.Br.
22 (1986)
38,43;
CHEMTECH
15 (1985)
692; CA 104
CA 104
103314. (1986)
185643. 662
K.B.Sharpless,
663
M.G.Finn
and K.B.Sharpless,
247; CA 104
(1986)
A.Pfenninger,
Synthesis
665
B.E.Rossiter,
Asymmetric
666
Synth.
6198.
5 (1985)
185629.
664
(1986)
Asymmetric
(1986)
(1986)
89; CA 104
Synth.
5 (1985)
(1986)
167667.
193; CA 104
167693.
H.B.Kagan,
E.Dunach,
S.H.Zhao,
C.Nemecek,
Pure Appl.Chem.
P.Pitchen,
57 (1985)
O.Samuel
and
1911; CA 105 (1986)
97058. 667
J.Tsuji,
668
S.M.Hecht,
669
R.H.Holm
670
P.Capdevielle 105
671
Acc.Chem.Res. and J.M.Berg,
(1986)
D.Mansuy CA 105
672
J.Organomet.Chem.
185907.
(1986)
19 (1986)
383.
Acc.Chem.Res.
and M.Maumy,
281.
19 (1986)
Actual.Chim.
363.
(1986)(4)
5; CA
171439.
and P.Battoni, (1986)
J.T.Groves,
3000
Bull.Soc.Chim.Belg.
95 (1986)
959;
225445.
Ann.N.Y.Acad.Sci.
471
(1986)
99; CA 105
(1986)