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Transition metal derivatives in organic synthesis annual survey covering the year 1977
187
TRANSITION ANNUAL
LOUIS
METAL
SURVEY
DERIVATIVES
COVERING
THE
IN ORGANIC YEAR
SYNTHESIS
1977
S. HEGEDUS
Department of Chemistry, Colorado State Fort Collins, Colorado 80523 (U.S.A.)
University
CONTENTS I. General
Comments
II. Carbon-Carbon
187
Bond
Forming
188
Reactions
A. Al kylation
188
B. Conjugate
22c
Addition
230
C. Acylation D. Oligomerization
241
E. Rearrangements
252
III.
Oxidation
259
IV.
Reduction
268
V.
Functional A.
Group
282
Preparations
282
Halides
B. Amides,
Nitriles
C. Amines,
Alcohols
D. Ethers,
Esters,
284 285 %86
Acids
E. Heterocycles
28-i
F. Miscellaneous
300
VI.
Reviews
301
I.
General
use
Cements
annual
survey
of transition
metal
This
It is not
covers
literature
intermediates
a comprehensive
*Annual Survey covering Vol. 143(1977)309-383 References P. 303
the
review
but
the year
for
for
organic
is limited
1976
see
1977 dealing synthetic
to reports
J. Organometal.
with
the
transformations. of discrete
Chem.,
188
systems that lead to at least moderate yields
of organic
compounds, or that
allow unique organic
low yields
are obtained.
Catalytic
transformations,
reactions
that lead cleanly
extreme conditions
are also
The papers in this than by organometallic ested
in the organic
Specifically Also
since
excluded
are
systems unless reports
survey are grouped primarily reagent,since
are papers dealing
structural
The number of papers reviewed reactions, to a lesser
extent,
for
A.
of
synthetic
in this
reproduction
application.
of
since
the
this year is roughly
twice
more efficient
and solid
the growing activity coverage
Finally, patents
reported
are
results.
that of last
in the areas of carbon-carbon
reflects
series.
organometallic
bond forming
phase
supported
in these areas and,
of the literature.
Al kylation
Organocuprates of a variety
continue
natural
to be extensively
products.
discrete
Subsequently,
of lithium
by IH NMRand molecular
existence
methylcuprates
association
of LiCuz(Me)z,
In general
solvent
CZ].
borane resulting
tyl ides,
ha1 ides
reacted
propyl
with
a variety
Cyclopropyl
by treatment
cuprate
3).
[IS].
product
phosphine.
while
4) El.
vinyl
cuprates
from trimethylsilylacewith retention
Similarly,
2) [4].
lanes
of conA cyclo-
rem dihalocyclo-.
This procedure
was.used
to synthesize
An asymmetric cross
coupling
of phenylmagnesium
was effected
using nickel
The use of the (R)(S)ohosphinegave
theuseofthe
Cl].
Li2Cui4e3 was most
by RX (eq.
was claimed as an intermediate. (eq.
solfor
to produce trimethylvinylsi
with BY,CuLi followed
bromide with 4-bromo-1-butene ferrocenyl
of
bromides were alkylated
propanes were dial kylated and sesquicarene
in ether Evidence
Trimethyl silyl
formed by exchange with the vinyl 1) C37.
data.
LizCuMea and LiJZu,Mes with alkyl,
ha1ides were studied.
and THF was the superior
figuration
the a?kylation
of LiCuzMea and LizCusMes was obtained
the reactions
cycloal kyl and aryl
(eq.
for
substrates, with much activity in the development to the synthesis of reagents , and their application
The composition
vents was studied
reactive,
exploited
of organic
of new organocuprate
(eq.
metal catalyzed
survey
studies
it.
Carbon-Carbon Bond Fonning Reactions
II.
the
with transition
asymmetric homogeneous hydrogenation This increase
type rather
to be more inter-
have not bee? surveyed
to allow
with most of the increase
by reaction
is likely
by another
data useful
literature
detailed
catalysis.
and do not involve
than the metal causing
and mechanistic
they present
sufficiently
year,
the reader effected
these are covered
from the patent
rarely
to a major product
included.
transformation
excluded
hydrosilation,
even if
(S)(R)
phosphine
produced
chloride 34%eeof
34%eeof
sirenin
and a chiral the(R)
the (S) product
189
RCsC-SiMe3
+
(cyclohexyl),BH
R
SiMe,
H
B(cyclohexyl)2
+
(1) R
X
SiMe,
-
H
P(OEt)q HMPT '
-
R'X
CU
R = m-C6H13-, -(CH,),~THP, CH,OTHP R'X = MeI, ally1 X, etc.
;', $-,CuLi ~
R2
R3
(2)
R3 RX =
RI = H, -(CH,),-
Nr3
MeI,
wBr,
R2 = Ph, H, cyclohexyl, PhCH20CH2 BrCH2COOMe, n-CfiH176r
R3 = H, Ph, Me R'+ = H, Me,IVfi CH3
X
X X
Cu-Li
Rl,CuLi
t
61
R
R2
cu
R R1
2+-
R = Ph, n-hexyl, PhCHzOCH2 R1 = n-Bu, s-Bu, t-Bu R2Y = MeI, EtI, CH,COBr, EtOH
References
p_ 303
Rl
R2Y l
J+ 60-90:
I90 Cl
Cl 1) (tle?C=CHCHpCH,& CuLi 2) Me1 3) H2S04-Hz0
ti
OuO
I
I 0
?Q
44% (3) NaH (MeO),CO
-
d,l sirenin
l
MeOOC
CHz=CH(CHZ)zBr
+
d,l sesquicarene
--
PhMgBr
+
NiClz
f
*P
Et70 r rfx 46 hr
CHz=CHCHMePh
(4)
16-58% yield 34% ee
iPha (R)(S)
or
(S)(R)
The alkylation of o-bromobenzoic acids by stabilized enolates was accomplished C71.
in
high
yield
using
sodium
hydride
and
cuprous
bromide
(eq.
5)
Terminal arylacetylenes were synthesized by coupling -in situ generated
72% COOEt
COOEt ,
RiH ;OOEt
,
also work.
and 0
copper acetylides with aryl iodides (eq. 6) [IS]. Vinyl zircona&, hydrozirconation
from
of alkynes, were coupled to aryl halides to produce styrenes
19: using a nickel(O) catalyst. internal
TMSCECCU
only
Terminal alkynes reacted in high yield 35% yields
?I BuLi 2)
HC-CCH(OEt)2
and
ArBr
Br
ArX
gave
alkynes
(eq. 7) 19-J.
In a similar
while
fashion
ArI
(6)
PY
failed.
I
=
R=H
71%
R = p-Me
45%
R = m-Me
50%
R = p-OMe
50%
R’
H
H
ArX Ni(0) cat.
R’CXH
(7) H
Cp,ZrCl
Ar
75-992 R' = n-pentyl.
EtO,
n-Bu,
THPOCH,CH,-
Tolerates COOMe
unsymmetrical L,Ni
biaryls
or LzPdClz
or magnesium
halides
symmetrical palladium nesium lyzed
failed
nitro,
[12].
(BrZnCHzCOOEt)
methyl-, copper(I)
with
iodides
by treatment
phenyl-,
benzyl-
salts.
Use of
trialkylboranes
with
tetraalkylborate
to replace
complete
retention
p.
303
the
with
iodides
and
CN and
group.
yield
by the
or benzyl
halides
acetyl
with
by the
aryl
mag-
palladium(O) at
100".
groups.
were
of the
Un-
in 80-92;; yield halides
zinc
cataThe
Chlorobenzene
prepared
Reformatsky
by the reagent
[13]. with
retention
n-butyl-,
led
with
of stereochemistry
i-propyl-.
reagents
with
the
stereochemistry in the
to polymers
followed
reacted
of
n-pentyl-,
or allyl-Grignard
halide
aryl
by the
acids
coupling
vinyllithium
These
aryl
phenylacetic
alkylated with
of aryl
o-methyl
methyllithium
salts.
acrylate
Rderences
aryl were
prepared
coupling
catalyzed
in high
with
were produced
chloro,
Finally,
or paliadium(0)
yield
were
of allyl-tri-n-butyltin
to react
Vinyl
cross
prepared
halides
OMe,
homocoupl ing was observed.
fluorine
Allylbenzenes
tolerated
nickel(O)
50-702
catalyzed
[ll].
were
of aryl
Very 1 ittle
containing
chloride
reaction
diarylmethanes coupling
[lo].
biaryls
halides
reaction
and
catalyzed
Cl,
on aryl
by cuprous
cis
alkyl
Cl57.
(not The
the
presence
1141.
of
produced
copoer-
&branoethyl
methyl)
reaction
of
Treatment
iodide
and trans
in
t-butyl-,
of
group
with
e-haloenones
192
with
a a,o-bis
1,4iaddition
cuprate
duced by treatment reacted
led
and alkylation
with
of the
alkynyl
produce ene-ynes
zinc
to the
bis
cuprate
+
Ia
of Spiro
(eq. with
8)
compounds by combined
[16].
acid
Diketones
halides.
in the presence
halides
in high yield
WC1
production
of a halide
Vinyl
(eq.
catalyst
to
9) [177.
O
-
RvR
halides
of a palladium
and high stereospecificity
R
were pro-
-A&
U
R
60%
Ib I
Li(L)Cu-(CR,),-Cu(L)Li Ia Ib
n=4 n=5
R = H, Me
R
(8)
&R 40%
60%
x
R!
RI
P3 +
R=
Cl ZnCXR4
P3
+X
5% Pd cat. O-25”
-
(9)
R’
X
X = Br, I
CaCR4
-80% yield
R1 = H, n-Bu, R2 = n-Bu,
COOMe
H, Et,
297% stereospecific
Me
R3 = H R& = H, n-pentyl,
Aryl
and alkyl
in the presence with y&
n-Bu
Grignard
reagents
coupled
of Ni(Ph2P(CH2)sPPh2)C12 (eq.
bromotrimethylsiloxyalkenes
a nickel(O)
cleanly
catalyst,
was also
produced by treating
with
&b’romovinylethyl
10) Cl8-i.
A similar
successful
[19].
nickel
ether
coupling
Finally,
bromide with butyllithium,
193 promoted the reaction between lithium ester enolates and vinyl halides (eq. 11) c207.
RMgBr
+
Ni(diphos)Cl,
BrCH=CHCEt
+
RCH=CHOEt
(10)
53-773
(711
with
LiCH,COOt-Bu
Phi
73x BrW
ggz Br
PhBr
94%
41%
olefin stereochemistry maintained
A T
60%
phASr
B3Yi
Sr
LiMeCHC02t-Bu
+
53x
B*
LiMe2CCOOEt
+
Liw LiPhCHCOOEt
+
Allylic alkylating
Phi
produced
CHz=CH-, ofallyi
isomers
halides
were
complexes quinones
+
Sr n
with
bis
ketal
methyltrialkylborate
was
salts
complexes,
Hith
borates.
observed,
allylammonium
presence
of copper(I)
of the
complete
agents
465
while
3-chloro-
propargyi
reacted
with
haiides
a variety
Ph, PhCH2, Me(CH2)7C=CH2, MeCH =CHCHp,
displacement
alkylated
quinone
alkyl,
in the
as alkylating via
transposition
(C2-7
HCXCH,) with
by copper
or 5-chloropentyl
Quaternary
[Zl].
reagents
HC-C-,
alkylated n-octyl,
allylic
aiienes
of Grignard
were
n-hexyl,
1-phenyproo-1-ene,
COOEt
46%
halides with
72::
Bw
[23].
salts
trialkylamine
allylic A very
alkylation
group
rearrangement neat
has
mixtures
[22].
Allylic
using
synthesis
recently
to give
of
been
RCu.SFs
isoprenoid
developed
(eq.
12) 1247, and involves alkylation of a vinyl cuprate. a-Bromoacids and esters were cleanly alkylated by methyl, ethyl and isopropyl ctipratesC251. Tricyclo[3.1.1.03~6]heptan-6-yl produced
in the
reaction
8’ tetrabromoacetone were
alkylated
References
p. 303
derivatives
of cyclopentadiene
(eq.
by n-heptyl.
13)
1267.
n-butyl
were
prepared
iron
tricarbonyl
B-Bromoethers, and
cyclohexyl
from
acetates Grignards
compounds
with and
CL,U',S, alcohols
in the
presence
prenyl
92%
geranyl
96%
phytyl
93%
0 + Br,CHF-CHBr2
---f--f
-
Fe(W)3
(73)
of 5% cuprous
iodide.
t-Butyl
Grignards
failed
acetates but reacted well with the alcohols
[27].
to react
with the ethers
and
The chromium tricarbonyl
group was used to both activate and alter stereochemistry in the alkylation of arylacetic esters Alkylation of cyclic
by phase transfer catalysis and sodium hydride. ester complexes is stereospecifically exo (with respect
to the Cr(CO)s group)
while
acyclic
stereoselectivity
(eq.
benzylic
a-haloketones
dienyl
halides,
14) 1281.
analogs Finally,
undergo alkylation cyclopentadienyl
and pyrylium
with less
copper al kylates
ion to introduce
a cyclopenta-
group C29-J.
Several new methods for the conversion of acid halides to ketones have been devel aped. The rhodium(I) complex L,Rh(Cl)CO was anchored to a phosphine containing
polystyrene
to produce the alkylrhodium(1)
resin,
treated
complex,
with n-butyl
which then reacted
or phenyllithium with an acid
195
olof,,,
Cr(CO)F, r
m"Me
P&C r
Cr(COjs (14)
OMe
Also
3 03 \
&,$
studied:
COOMe
RX = MeI,
halide
BzBr,
to
produce
supported
ketone
system
ly reported and
both
Br
e
was
Only
n-hexyl. ketones
were
by Z" alkyl
purified
reacted
in 75-92X yield.
The
one
the to
with alkyl
of the
prepared
aroyl groups
with
RCOCl
-I- R'R"CHCu
7
0
and n-butylacetylenewere
Ally1
L,PdC12
ketones
and
were
allyl-trimethyltin alkynyl
ketones
manganese(I1) aldehyde
ReGxencesp.303
acylated cuprous
prepared with
were
and
ketones
were
resulting
with
a variety
catalyst
[313.
ketone,
and
15)
of acid
as a catalyst treatment
underwent chlorides by the
competitive were
reaction
amine
[34].
of acid
Phenyl
F1 /R' R-C-C-R" A#,.
_
acid
c331.
with
alkenyl
and
with
organo-
alkylation
polymerized
16)
halides
Alkyl,
(15)
by treat(eq.
chlorides
of acid
halides
alkylation
[32].
halides
in triethyl
and
Ditertiary
of acid
R,"CuLi
by treating
methyl-
i-butyl
I&
by the
acid
f
lower,
alkyl aryl ketones
alkylation
(eq.
R' 0 " / RC-C-R"
+
in 37-86": yield
produced
the
previous-
were
n-butyl-
transferred
alkylcuprate
iodide
Aldehydes
conjugated
groups
of the
ClRh(PPhs)s
prepared
iodides.
group
Symmetrical
to produce
This
the
Copoer(1)
[30].
n-propyl,
R' LR"
filtration
involving
than
the yields
chlorides
a different
R-;-CH'
although
were
complex.
to use
used
alkyl
bromination
cuprates,
a-haloketone
with
by simple
three
chlororhodium(1) convenient
system,
by a sequence
of the
ment
starting be more
homogeneous
were
trialkylborates
and
claimed
identical
systems
, HC-C-CH,Br
at the
C351.
chlorides
with
196
0 R+CH
+
0
LpPdClT/ CuI,EtsN
R2;-Cl
k
RIC=C-t-R2
(76)
60-961 RI = Ph,
n-Bu
R2 = Ph,
PhCH=CH,
- Fez(CO)s this was
in refluxing
reaction used
coniums, acid
formed
does
n-octenes
react
+
, NMe2
olefins
Fes(C0)12,
Transmetalation
with
acid
a rapid
acid
Cp2Zr(H)C1
and
from
chlorides
hydrozirconation
give
with
Fe(CO)s,
[36-j.
by the but
i-Pr,
ether.
to occur
to acylate
chlorides
which
t-Bu,
(eq.
of olefins,
transmetalation
Co2(CO)a
zirconium 17) are
[377. not
to aluminum
do not
cause
to aluminum Alkyl
reactive
zirtowards
trichloride
chlorides.
+
Cl Cp,Zr-n-octyl
AICll o0
+ Cn-octylA1C127,
CH2C12 (17) 0 R'COCl
l
R:-n-octyl 98%
/c s
EtooC\C’CooEt +
LizPdCl,
+
NaCH(COOEt),
THF ZSO f
/ ‘r
SjPd\
A (NMe)z
(18)
91%
1) LiTPdCIL, 2) NaCH(COOEtj2 31 Hz
(191
f :::::\N, 90%
\
1) Li7PdClr, 2) NaCH(COOEt)2 '
b
Pd-N
(20)
0
l
2:l DMF-PhH
0A
EtOOC
\
COOEt
Cl
COOEt
-
-
Prostaglandins
35% overall from
References
r. 303
0/ \
The
direct
by several
alkylation
palladate
and
stabilized
complex.
The
organic
(eq.
18)
fins
failed
enolates
amines
to alkylate.
led
was
alcohols
(eq.
19)
This
C391.
prostsglandin olefins (eq.
precursor
could
21)
(eq.
be alkylated
[41]
or
ethers,
successfully
Fe(CO),
was 20)
used
22)
and
carbanions
ole-
ketone Homoal lylic carbanions
synthesis
using
full
simple
by stabilized
elegant
appropriate
The
[42].
reported chloro-
borohydride
and
alkylation.
alkylated
Under
by stabilized (eq.
than
in a very
[40].
sodium
esters
organocuprates
rather
been
lithium
o-alkylpalladium(I1)
with
conjugated
reagents,
has
with
a stable
by reduction
of palladium
chemistry
carbanions
reacted
to produce
and
amir-tesand sulfides were also
soft
sulfides
freed
Grignard
to reduction
with
and
carbanions
ligand
Ally1
C381.
of olefins
Ally1
groups.
of a
conditions
simple
palladium
chloride
experimental
details
of
COOEt R COOEt +
H2
PdCl,(CH,CN),
+
f
2 EtsN
+
/
LiCH(COOEt)2
(21)
COOEt
j3-elim. \
R OOEt
II
-Fe(CO),
the
+
1) TFA 2)
EtCH(COOEt)z
(22)
68X
addition
olefin
of stabilized
complexes
cation
ed 1437. cuprates
The and
paper ylids,
allylpalladium (eq.
THF o0 b
cH(COOMe)2
23)
of key
covers and
complexes
[44].
A series
intermediates
reactions
studies
carbanions
to
produce the
has
to cyclopentadiene
stable
addition
extensive
in allylic
of enolates, tables
by stabilized of new
a-al kyl iron of data.
carbanions
n-allylpalladium alkylation
have
has
iron
enamines, The also
complexes been
dicarbonyl
complexes
have appearGrignards,
alkylation been for
synthesized
of TF-
reported use
as models
and
their
[45].
COOEt (Pd<>
2
+
CH(COOEt)R
(23)
' EtOOC
i
COOEt R = CN
Me7S0 THF
70%
R = SO,Me
52%
R = COOEt
quantitative
199 Palladium catalyzed fins
in the presence
Acetylene
reacted
and palladium onitrile,
Iodoferrocene
of palladium
cyanide catalysts
gave mixtures
of both positional
went Mith methyl vinyl moderate and side was phenylated in the presence arylation
resulted
[47].
as a mixture
The reaction
to arylation
but
The reaction
also
oxide, but yields were only The dimethylacetal of acrolein acetate
and tri-o-tolylphosphine
of the dimethyl
of acryl-
of the olefin
isomers.
with bromobenzene using palladium(I1) of triethylamine
iodide
with bromobenzene and
and geometric
ketone and mesityl
products
of copper(I)
acetyl ene C461.
led predominantly
of ole-
to produce al kenylferrocenes.
in the presence
and methacrylonitrile
palladium(I1)
continue
with a variety
was reacted
acetate
with iodoferrocene
to produce diferrocenyl
ally1
and arylations
“Heck” type alkylations
to be used synthetically.
acetal
as a catalyst
to give
of cinnamaldehyde
up to 98%
and methyl-
2-phenylpropionate C49]. Styrene was converted to trans 902 yield by reaction with methyllithium using Pd(scac)2 reaction such
consisted
of a cis
addition-cis
a-methylstyrene in as a catalyst. The Substi tuents sequence.
elimination
as p-C1 (90%)) m-Cl (80%) and p-Me(60Z) were tolerated,
as sodium diethylmalonate,
[49]_
Kinetic
studies
sence of palladium(II)
only a low yield
on the arylation acetate
of
to form trans
of ethylene
carbanions
alkylation
of styrene
(a)
such
PJas observed
by benzene in the pre-
stilbene
mation of a u-complex was the rate limiting step EOI.
were formed by the reaction
but p-OMe sub-
With stabilized
stituted styrene led to low (15%) yields.
with thiophene,
indicated
that for-
Vinyl heterocycles furfural and furan
in the presence of palladium salts [51]. Vinylidene chloride reacted with isobutene in the presence of palladium(I1)
ArNHz
-f
r
+
Ph
ArNz +
olefin
+
Pd(0) cat.
-+
Ph
(24) 57%
References
p. 303
200 acetate
at
in GO%
yield.
60”
to oxidatively couple, producing l,l-dichloro-4-methylpentadie Nitrite was found
to suppress dehydrodimerization
of iso-
butene r-521. Palladium(O) complexes were used to catalyze the arylation of olefins by qromatic diazonium salts.
Ally1 alcohols led to phenylalde-
hydes (eq. 24) C537. Styrene was also directly arylated by anilines to produce stilbenes using palladium(I1) acetate.
The reaction involved C-N bond cleavage [54].
by using a chiral copper complex to catalyze the decomposition of alkyldiazoacetates,
trans-e-menthyl chrysanthemate was prepared in 72%
yield and 94% ee (eq. 25)
C551.The
bulkier the alkyl group of the diazo
,COOR 7.4% cis 89.9% trans d
94% ee(25)
2.7% trans e R = 2,3,4-trimethyl-3-pentyl
Rz = 5-t-butyl-2-octyloxyphenyl
catalyst =
@CO'"""
+
O/CH?COCOOEt
76%
Rh,(OAc), / NzCHCOCOOEt
+ 0
(26)
I
0
07
COOEt 79%
compound, the more trans the trans
isomer.
tuted olefins complexes
product
was formed,
Cyclopropanation
in the presence
reactions
and the higher was the ee of of diazoalkanes
and absence of nickel(O)
of the type M(Me3CNC)2or M(PPh3)2(CzH,)
with substi-
and palladium(O)
were studied
and inter-
mediate complexes were isolated and characterized by x-ray crystallography The reaction of ethyl diaropyruvate with cyclohexene Produced drast567. tically
different
products
when Rhz(OAc),
was used as a catalyst
than Ti-allylpalladium chloride (eq. 26) C57J. Olefins were alky?ated by isonitriles via s-allylpalladium
rather complexes
Isonitrile complexes were intermediates or a-alkylpalladium complexes. a,B-Unsaturated chromium carbene complexes underwent 1,4(eq. 27) C583. alkylation by enolate anions (eq. 28) C591. The role of puckered
\ 0
PdCl 3 h
OPdp
.+
(==+=N-t,u
(27)
MeOH NazCOs ’
Cr(CO),
f
MgBr
CH90S07F >
(C0)sCr !l%
metallocyclobutanes of cyclopropane
(from metal carbenes
formation
was studied
and olefins)
by the --in situ
OMe
in the stereochemistry generation
of
(CO)sWC(Ph)H c601. The [2a + 2x1 cycloadditions catalyzed addition
by palladium(O) products
Referencesp.303
of methylene
cyclopropane.to
alkenes
complexes were found to give mixtures
and cyclodimerization
products.
Unstrained
of cyclo-
olefins
and
202
0 Ce
(CO)sCr
Me0
4+
*
(28)
% 73%
p\&?sL
79%
*.
+&)
I
40%
OMe
20% 82%
l- or tion
P-alkenes metal
were
catalysis
K
unsuitable has
(eq.
29)
Olefin
insertion
in transi-
been reviewed [62].
recently
Pd(0) cat. loo0
-i- RCH=CHR'
1617.
~
R
+ p
(29)
23-94% O-782 The
effect
of solvents
and
lithium
salts
on the
addition
of
lithium
alkylcuprates to l-alkynes to produce lithium vinyl cuprates has been studied in detail.
Lithium
dibutylcuprate
at
greater
than
C-2
the
with
regioselectivity
without
was
addition. were
than
stereospecificity
98%
prepared
by treatment
succinimide chemistry
was
was the best was
for
duction
of
complexes [67].
The
chemistry used
bromide
from
by the
and
group
terminal
C641.
90% yield
[RCuSr~Mg! N-bromo-
the
study
found
that
Vinyl
greater
iodine,
Essentially
it was
alkyne
1631. and
alkyneswith with
In a general
C651.
alkynes,
the
deprotonation
than
of terminal
30)
[IRCuIlLi
deprotonated
vinylcuprate
(eq.
phenylacetylene terminal
branched transferred reaction of addition
in a synthesis
this
1-octyne
with
same of the
CRCuBrlMgCl
for the introduction of 1" alkyl (R) groups into ace-
reagent
other
simply
in greater treatment
and
In contrast,
R2CuLi
thus-formed
by another with
to phenylacetylene
suppressed
alkynes
of the
reported
propyne
best
In THF
or N-chlorosuccinimide
reactivityof[RCuYBgX
tylene,
added
regioselectivity.
lost.
Lithium
bromides
followed
90%
chain only
(forming
alkynes. alkyl
groups
one
R group
of eneynes depended of myrcene
with
[66]. and
nature 31)
Ct-BuOCuRlMgX
good
for
It was
that
RzCuMgX
more
was of R.
C687.
while
particularly
were
CRCuY7MgX
on the (eq.
RR'C=CH2)
THF was
found
reactive
also
than
studied.
This
chemistry
intro-
CRCuBr7MgX
The
regio-
was
.
203
R'C-CH t
CRCuBrBgX
R = Et, i-Pr, cyclohexyl, t-Bu, n-Bu R' = Ph, Me, Bu, H
R,C=C-C-CH +
X = Br, I, Cl
>90%
XY = NBS, NCS, I2
[R"CuY]MgX
-
H+
;il
R2C=C-C=CH2 + i,RI,
>9B% stereochemistry
/H R2C=C-CH=C \R" r;,
a
b
R" = 1" al kyl , >95% a R" = t-Bu, 1:1 a to b (31) =-=f -
CuMgCl -
-
H+
90%
myrcene Thereactions of propargyl alcohol with EtCu and with EtMgBr in the presence of copper(I) salts were compared. In ether both reagents added trans to place the metal on the terminal carbon, while in THF, a cis addition occurred (eq. 32) C691. Similar studies were carried out on the corresponding
allenic
alcohol.
The intermediate vinyl magnesium halide was fur-
ther Functionalized (eq. 33) [70]. Cumulenic ethers reacted with Grignard reagents in the presence of cuprous bromide catalyst to produce eneynes (eq. 34) C717. Use of discrete [RCuBr]M complexes led to reductive alkylation. Propargylic ethers, sulfides and amines reacted with organocopper species in an addition reaction whose regioselectivitydepended on the nature of the heteroatom (eq. 35) C721. The chemistry of the vinyl cuprate intermediates was also examined.
ii""
H&C-CH,OH
References p. 303
c)=(E:,oH
(32)
204 RCH, CHz=C=CH-CHzOH OH
(33)
OH
R = Me,
Bu,
i-Pr,
Ph
R'R"C=C=C=CHOMe
i-
10%
RMgX
CuBr
f
RR'C=C-CeCH ; 80-902
[R"'CuBr?MgX
(34)
I RR'C=C-C=CHOMe R,,,
R = alkyl, R',
Ph
R" = H , Me R
RCu
+
R'CrC-Z
-
R'=H
CH
n-Bu 1
Terminal hydroboration catalyzed
chloride, The l-01
were
alkynes with
were
were
lithium alkynols ethylated
R'=H
converted
of the coupled
chloride
and
3-butyn-l-of.
to trans
hydrides vinyl
(eq.
to halobutadienes oxygen
in acetic
3-pentyn-1-01,
by diethylaluminum
NEt2,
disubstituted
followed
borane
n-Bu
chloride
\
, n-Bu , Me
Z = OEt,
dialkylboron
decomposition alkynes
R = Et,
b
-No a
3
Z = SR'
terminal
77-95%
(35) Z
b
a R = n-heptyl.
X
R'
Z
R'
H
-
t
b
alkenes
by
by palladium 36)
C737.
acid
(eq.
using
bis
37)
a
acetate
Styrene
by treatment
4-pentyn-Z-01
54-92s
No I NPhz -
with
and palladium
[74]. and
4-pentyn-
cyclopentadienyl
205 H
R RCXH
-i
R2’BH
R
+ H
H
)_(-
Pd(OAc):, EtsN THF
(36)
H
R'
58-98X R = Ph,
t-Bu,
Cl(CH,),-
R' = CHMeCHMe,
PhCH=CH2
+
R = Ph,
n-Pr,
titanium minal
cyclohexyl,
PdC17, LiCl 02, AcOH
RCXH n-Am,
internal
3-hexen-l-01
as a promotor.
and/or of Jo&
pargyl
alcohols
were
38)
(37)
on alkyne
50-24002
on Pd
Terminal
alkynes
3-pentyn-l-01
acetylenes
trialkylbenzenes
presence
involving
while
Terminal
in the
sequence
PhCH=CHCH=CCl-R 40-60X
ethylation
C757.
1,3-butadienes
k
Et
dichloride
and
Z-methylcyclohexyl
were
underwent
gave
converted
by treatment
to
alkylated
by aromatic of the
bond
trialkylaluminums
C761.
hydrocarbons
triple
ter4-methyl-
(E)-2,4-dialkyl-
with
(N-methylsalicylaldimine)nickel
protection
both
exclusively
Finally,
through
as a cobalt
an
pro-
unusual
complex
(eq.
t777. R2
R2
R3C-C-C2H
co7(co)R
+
R3_C_C-&)H
‘,, \
:
R’
,R’ -
Hf
R3-C=_C-C+ a’ ‘> \ ’ ‘.
RI
; ,to (CO),Co
RI
(CO13
(38) R3-C-C-C-R2
/
RI o,p
\
ratio
depends
on acid
used HBF4.Me20
40%
+
78%
p only
I
OMe Transition The
oxidative
metals coupling
chloride
was
hydrogen
coupled
yield. having
References
carefully very
Substituted two
different
p. 303
continue
to be extensively
of ketone
enolates
studied.
Ketones
well.
methyl
Methyl
hydrogens
for
to 1,4-diketones with
ketones
ketone's coupled
enolizable
used
a single
coupled in very gave
coupling
by copper(I1)
type
of enolizable
in moderate low yield.
mixtures
reactions.
but
to excellent Ketones
the
!east
hin-
Olefins, cyclopropanes, ferrocenyl and
dered 7,4-diketone predominated. ester functionality was tolerated.
Attempted cross couplings gave all
possible products but two different methyl ketones were cross coupled in Intramolecular couplings
moderate yield by using a large excess of one.
of diketones failed except for diacetyl ferrocene [787. using copper
This reagent also coupled
triflate has also been reported.
trimethy7silylenol
Ketene silylenol acetals were coupled to
ether: C79J.
succinatesbytitanium
Similar chemistry
tetrachloride
(eq. 39) [807.
Osmium(IV) salts coupled dibenrlidene acetone to produce a cyclopentanol product (eq. 40) C817, while palladium chloride dimerized ethynyl vinyl ketones (es. 41)C821.
R'R'C=C
,0R3
R1R2C-COOR"
TiCIL, .
(39)
I
R'R2C-COOR3
'OSiMes
73-80%
PhmLPh
+
In
i
K2 OsCl 6
pheH=CHPh
+
(40)
Ph
COCH=CHPh 100%
R’
0 R'CH=CH:-CzCR2
R2
PdC13(PhCN)7 PhH, A
\ 3+
R2
CH2R1
f
0 (41)
OH
R2
R1 = Ph, RZ = Ph, mesityl CH2R1
R1 = Me 3 R2 = Ph RI = Ph, R2 = Ph, Me RI = Me, R2 = Ph, Me, Et
Reduced titanium species have proven useful for the reductive coupling of ketones, aldehydes and diols. in hiah yield
by cyclization
with a titanium species
Large ring (Cl,- C1s) olefins were prepared
of the corresponding
resulting
a,w-dialdehydes
or ketones
from the reduction of titanium trichloride
207 with zinc-copper by this
route
dineopentyl
couple. (i.e.,
ring
cyclic
olefins
1,2-diphenylcyclobutene,
ketone,
to symmetrical
Small
could
87%) CS3J.
adamantanone and dicyclopropyl
olefins
by TiCle/py,
produced
also
be prepared
Ketones,
by reduction
of Tic14 with zinc. The rea-
Unsymmetrical ketones gave mixtures of geometrical isomers C841.
gent resulting
from the reductionof
aluminum hydride
coupled
the appropriate
(61%) and 1,2-diphenylcyclohexene coupled
to give
Benzhydrols heating
a mixture
of cis
were reductively
A variety
1.2-diphenylcyclopropanes
halides
with a reagent
benzyls
and vinyl
dihalides
halides
to the corresponding
of RuCl,(P?ha)s.
products
J@
were coupled
bromides
were coupled
to biaryls
to give
with zinc,L,NiCl,
was synthesized
by treatment
than cupric derivatives
(eq.
coupling
chromium(II1)
chloride
were coupled to biwith VCl JLiAlH;, while
al kenes [881. Aromatic (PhBr,89%, e-MePhBr, 73X, p-MeCOPhBr, 581,
and excess
by copper(I)
Grignard reagent
possible
c861.
of halides.
to the corresponding
e-Me02CPhBr, 831, e-MeCONHPh, 37%, o-tolyBr, treatment
all
coupling
by
pal ladi urn
from benzhydrols
the reductive
Benzylbromides
to dienes
1851.
hydrocarbons
The corresponding
formation
formed by reducing
[87].
were dehalogenated
to 1 ,2-diphenylcyclobutene
and trans
promoted only ether
aluminum hydride
with lithium
1,3-Diphenylpropane-1,3-diol
Unsymmetrical allylic with lithium
diketones
of metals have been used for
by treatment
tetrachloride
(35%).
coupled
to 190” in the presence
and platinum complexes
titanium
including
ketone were dimerized
catalyzed
42) c901.
12C, 2-brcmothiophene,
phosphine coupling
Cuprous
41%) by
in DMFC877.
Pleiadiene of the appropriate vinyl
catalysts
were found
more effective
catalysts for the Ullmann condensation of haloanthraquinone with amines in aprotic solvents cgi7.
Br
1) activated Mg 2) CuBr, -500 to 20”
(42)
l
Br 45% Pleiadiene Diary1 ,
al kynyl , vinyl
and benzyl mercurials
to produce the corresponding HMPAat 50-130”. Em. Similarly, dienes
Symmetrical tion
v;-iylmercuric
by treatment
Aryl mercuric
hydrocarbon
Di2lkylmercurials
halides
dimer by treatment
did not couple
halides
coupled
with BHzCl-OEtz followed
to biaryls were also
and lithium under these
prepared
by treatment
coupled
with LjRhCl in
under these
were catalytically
with rhodium catalysts
(E,E)-1.3-dienes
were catalytically
conditions
coupled chloride
conditions
to 1,3-
in HMPA. [93].
from al kynes by hydrobora-
with methyl copper
(eq.
43).
208 R’
R R&CR’
f
BHzCl:OEtz
-t
(43)
EE
>99%
R = n-Bu, R’ = H 93%
R= R’ = Ph
R= R’ = Et
99%
R = cyclohexyl.
R = R’ = n-Bu
95%
R = Cl(CH2)s,
“Ate” complexes of a variety
were implicated
of aryl
45% R’ = H 71%
as intermediates
copper aggregates
99%
R’ = H
[94].
Selective
coupling
was explained in terms of intraagcjregate electron transfer processes 1957. In the cross coupling
of aryl
reaction
was shown to proceed via Ar,Cus(C=CR)z
II
Q’- ’
cu
copper
species
to form biaryls
”+
with alkynyl
DMF 175” l
CuC-CR
/
copper
_
\
9,
NMez
complexes
clusters,
(eq.
44),
the
which were iso-
C-CR
(44)
Mez
76-92% R = Ph, p-tolyl, lated
2,4-xylyl,
L,3,6-mesityl,
and characterized.
cluster
contains
Selective
exclusively
and one al kynyl ligand Alkylbenzenes palladium
salts
triangular
were oxidatively
in heteropolyacids
by treatment
with palladium of aromatic
as have coupling
ferences)
ClOO7.
Catalytic interesting
coupling
acetate
anilines
acetate
alkylation
coupled [97-j.
occupied
by one aryl
C98-J.
to biaryls Palladium
with
to bifurans
catalyzed
oxidative
been reviewed (88 references)
metal complexes
were coupled
(500 re-
to 4,4’-diaminodiphenyl-
acetates
has accounted
Treatment of an allylic
using 1% Ll,Pd catalyst
60-98:: yields
alkylation
The same chemistry
by treatment
Furans were coupled
anion of diethylmalonate c1021.
because the
[loll.
of allylic
transformations_ of allylic
occurred
copper faces
compounds has recently reactions via transition
Dialkyl
methanes by palladium
cross
4-Cl-Ph.
[96].
dimerization c991,
4-MeOPh, 4-NO,-Ph,
several
with the
and 10% (+)DIOP led to
with 20-37% optical
was used to elaborate
for
acetate yields
(eq.
45)
COOMe
+
cH(COOMe)2
60-9s:; ZO-37% optical yield
0
! --_(46)
@ OMe
ecdysone
SO,Ph I
1) NaH 2 6% L&Pd rfx, THF
B-Diketones acetate via
assisted
a radical
allylic went
to develop
p. 303
[MeCuXlLi
or Sn2' the
were
with
ally1
where
pathways
with
obtained,
alcohols
[106I_
X is methyl,
depending
product
the The
cyanide
on X (eq.
a-alkylation
major
by the
to introduce
reported
acetoxyepoxides. with
COOMe
g!
terpenic
acetate
were
nucleophilic
reacted
was
from
No yields
with Sn2
of a alkylketone References
reaction
acetates
alkylcuprates
synthesized
pathway.
by either
attempt
were
l
(47)
49)
of ketones,
manganese(II1)
acetonyl
reaction
or thiophenoxide In an
ClO71. lithium
A maximum
yield
being
non
the
group, of
di-
of 43X alkylated
7) NaH 2) LbPd THF rfx 49-692
AcO (n = 1,3)
I exal to1 ide (sat., n = 3)
1) NaH 2) 20% L4Pd + HMPA/THF rfx diphos
0 Q
/ -
COOMe 45%
(45)
hum1 ene
ketone,
from a formal
elimination
ment of OH by R in allylic in eq.
50 [1091.
reactions allylic
Similar
acid [lOS].
The direct
replace-
was achieved
by the sequence described
chemistry
was achieved
using
of Grignard reagents transposition
of acetic
alcohols
with allylic
was observed
in this
alcohols,
(Ph,P)2NiC12 although
case [llO].
Allylic
catalyzed
significant l-perfluoro-
al kyl alcohols of the type CH2=CHCHRF(OH) reacted with iodobenzene in the presence of palladium salts regioselectively at the terminal olefinic carbon to give mixtures
of PhCH2CH2CORF and PhCH=CHCH(RF)OH [ill].
reagents
with monoallyl
reacted
phosphates
in the presence
bromide to replace
the phosphate
regioselectively
amounts of allylic
transposition
were noted CllZ].
reacted
under similar
conditions
to replace
Grignard of copper(I)
in 80-9056 yield. Ally1
sulfonium
Small salts
the R2S by the Grignard al kyl
211
[MeCuX]Li
OAc
X = Me
X
0”10
>95%
CN
=
OX
X = SPh
>957' 3
25%
75%
but
(49)
X = Me X = CN X = SPh
1) 2) 3) 4)
R-OH
-
with
OH,
CHaLi GUI R"Li [PhsPNMeTIPh
/--vo",
, PhCHOH,
R2 = BuLi ,
Li 0
on the
transposition
reagents
References
, MeLi,
were
iodide
p. 303
CH,OH
D-
set-BuLi,
PhLi,
EtLi,
BuCzCLi
double
bond,
S
Depending
of allylic
copper(I)
70-95:;
pvH,
CHs
nard
(50)
OH
v
group.
%
substitution were
selectively
(eq.
52)
on the
observed
[114].
(eq.
alkylated Geraniol
51)
[113].
by halides was
varying
Finally,
or tosylates
synthesized
amounts ally1
Grig-
and
in this
manner.
/
\ 40- 90% y i el ds 30: 70 1oo:o t0 (depending on R’s)
Rl R2 f\ I?3
\
MgX RI R”X/CuI
i
R’ ti
R
(52)
CHzOH I
gerani 01 4-t-Butyl
cycl ohexanone reacted
and MeLi-LiCuMe2 in ether than was obtained methylsilanes to give
with MeLi alone
reacted
high yields
Conjugated
also
ethers
effected (eq.
(eq.
55) [118].
aldehydes
to
promote
attack)
[115].
(eq.
to the carbonyl 53) 11167.
activity
con-
Chi ral atertiary center
between a bromoethylacetate
in higher yields
procedure
themselves
ketones _
in the newly-formed reaction
9roup.
and a,E,-(,&-unsaturate
Simple si 1yl enol ethers
the alkylation
attack
Allyltri-
Titanium
betwtzn acetals
to give 2-hydroxy-1.4-di
The Reformatskii
than when the traditional were used
the reaction
and ketones proceeded
amounts of equatorial
in the presence of titanium tetrachloride
by 1,2-addition
54) Cll77.
induced optical
(87-93)
(69% equatorial
with ketones of alcohols
densed with o-ketoesters ketoesters
wi th MeLi-Li Br , MeLi-Li I, MeLi-Li Cl Ok, higher
enones underwent 1,4-addition
tetrachl,oride silylenol
to give
was followed
using zinc-copper cll9].
and
couple
Chromium(I1) salts
of ketones and aldehydes
by allylic
haJides to give homoallylic alcohols. Coupling always occurred at the most substituted allylic terminus. Aldehydes were more reactive than ketones,
213
R 0
0-
’
R&;OR
TiClr, CH$l 2
SiMes
OH
0
/ ox
*
COOR ’
(53)
/ 70:: +A 0
OR2
R’
+
R3AOSiF,e
TiCIL
3
;
Rlwo
(54)
_( OR2 R3
RI
= Ph,
16%;
R2 = Me,
and
While
88%;
/=, Me
865.
7, ’ nPr
70%;
Et
ester
promoted
PhCH=CH-,
and the
many
cyano photo
substrates
tically
useful
reacted
groups
were
reaction
of
gave
ones
are
with
ketones
to
reacted
with
this
References
P. 303
reagent
low
tolerated alcohols yields
recorded give at
in
tertiary low
ClZO]. with and/or
eq.
56
tetrachloride
C=N containing
complex
mixtures,
Cl213.
alcohols
temperatures,
Titanium
C=O and
in
the
Alkylmanganese high
aldehydes
compounds. syntheiodide
yield.
Acid
at
moderate
chlorides tem-
214
Rz
RI
TiClrt CH&l
H70 r
l
R,Si'
0 R = Me,
R2 R3 0
Et
RI = Ph,
Me,
t-Bu
3
77-100% yields
R2 = H, Me
18-60%
R3 = Re, Ph
optical
yield (55)
RIO, ,c=c, YesSiO
0
AR2
f
0
I/
0 -
R3-&-;4-J
R2R30
&-&&;-_O
R'
x
R2 i)H
‘(1
83-88% R = Me, RI = Me,
H
R3 = Me,
Plr
peratures,
ketones
discriminate Isoprenoid
c1221.
at room
temperature,
between
aldehyde
hydroquinones
allyltrimethylsilane reaction
proceeded
(eq.
C1233.
57)
Epoxides using high
yield
amounts tives
in the
weFe
[IRCuCNlLi
reacted
with
with
the
cleanly
alkylated
expected
iodobenzene
of styryl
presence the
rather
yield
inert.
The
with
C1251.
a-Mono were
same
isolated
for
no need
in some
excess The
with
The cases
reagent
reactions
by went
in
Enol esters (acetates)
Cl241.
to produce
styrenes
or a,a'-dimethyl prepared
molecule
quinones
tetrachloride.
was
acetate
in the reaction
complexes.
regiochemistry
and palladium
acetates
the
reagent
and small
or phenyl
by addition
deriva-
tc excess
[126].
Oxidative variety
which
RaCuLi
were
groups
from
of titanium
quinol,
than
esters
and keto
through
salts
and
resulted
of p-tolylsulfonylhydrazones
R,CuLi
optical
Et
R2 = Me,
could
35-68s
t-Bu
phenolic
of natural
low yield.
Several
couplings
products new,
has
higher
to form long yield
been
polycyclic used,
processes
but have
skeletons proceeds been
common normally
developed
to a in
and
are
215
-j$- LOMe
_b’)--y)ob,
WCHO
H
H
45%
y-v
60%
(56) R
R'
R" N CH
Me@’
+-R
NHR” f
R’
CHpOH
‘OMe
95%
Me0
cupc13
PY, 0, *
tMe0 28% corytuberi
ne
(58) References p. 303
216
R' = COOlMe 3 Rz RI = COOMe, R1 = CN, (Worked
for
benzophenanthridines,
, R3 = OMe
75%
R? R3 = -OCHz-O-
85% 91%
R2 , R3 = -KHz-O-
methyl-picene-14-carboxylate,
OMe
also.)
OMe
OMe
OMe tylophorine
sumarized a model were
in eq. 58 [127l,eq.
ogidative
reported
in detail
Nucleophilic accounted chromium ly meta
for
coupling
substitution
of 2,6-dimethylphenol
The
soecifics
by copper
of salts
C1307.
aromatic
several
carbonyl
59 El281 and eq. 60 [129].
reaction
substitution
useful
reacted with
on n-arene
transformations.
with
a variety
less
than
The
chromium toluene
of carbanions
2% para.
Similar
complexes complex
to give results
has
of
predominatewere
obtained
with
anisole
(94-700%
was
bulky.
and
lithiodithiane
used The
to form
This
studied
C7317.
fused,
reaction
copper
meta).
Carbanions
An
Spiro
or copper
particularly
LiCHzCN,
intramolecular
with
powder
version ring
ethyl
resulted
true
when
LiC(CHs)zCN,
and metacyclophane
of N-methylpyrrole
bronze
was
were
of this
u and
carbanion
reaction
(eq.
systems
diazoacetate
in both
the
LiCHzCOO-t-Bu
61)
in the
was
C1321.
presence
B alkylation
of
of the
OR
HO VOCI? Et,0 -78O to +35'
RO
t
HO
(60)
HO
HO
HO \ COCHs
pyrrole
The ratio of isomers (a-
ring.
on the
metal
Grab
used
type
by copper(I) purified
used
material
(eq.
tion
to prepare
tricarbonyl
A!der steric
reaction. hindrance
tricarbonyl bridged References
p_ 303
and
crude
predominated)
chloride
cycl obutenes
was
to
The
reacted
synthon
energy
of the
(eq.
of the
substrate
underwent
compounds
with
dependent
(eq.
(eq.
66)
(eq.
64)
reaction 63)
iron
and
were
worked
65) Alder
[138].
[137].
pro-
cl351. tri carbonyl
by the
cyclobutadiene
than
between
8 la&one
ultimately
generated
promoted
better
was
cis,trans-
oxidation
2,5-di-t-butylbenzoquinones
strained
Diels
promoted
cycl obutadienyl
Cyclobutadiene,
[136].
rings
complex
and an unsaturated
1,3,5-cyclooctatrienes
complex,
six-membered copper
The nickel
C1341.
use as an isoprenoid of
complexes
bicyclic
62)
The
magnesium
a compound of
1 ,Scyclooctadiene
iron
of five-
trifluoroacetate.
Cycloaddi
always
[133].
fragmentations
trimethylsilylmethyl duced
50%
of
overcame
the
Cycloheptatrienyliron
reactions
with
The
palladation
ortho
TCNE
the
in a Diels
to give of
218
1)
43
(LiTMP)
N-Lif
(‘&)&HP
l
THF, -78O 2) oxidation 89%
Q/\
(CHa)&HzCN
dr(CO),
CN
1) O", 24 hr 2) Hi
72
28 (72%)
3
97 (70%) (61) CN
(CH,),CH,CN
1) LDA, O", THF. 2) oxidation
SPh
"h
w
(62)
CSPh
92%
benzylic tertiary amines was directed exclusively to either the 2 or 6 position of the aromatic ring, depending upon the substituent at C-3. Since these complexes can be functionalized at the palladium carbon bond, this procedure is of some synthetic interest C7391. Applications of a-ally1 transition metal complexes in organic synthesis has recently been reviewed (58 references) [140] as has organomercurials reagents and intemediates
in organic synthesis (235 references) Cl413.
as
219
Me$iCH$lgCl
0
+
NiC1y
r
Me$i&COOH
-Q95%
(0% without
v
Ni)
(63 OOH
-
LiN(SiMe?)?
Me3SiCH2
91%
ci R
&
R
I--
A
R
-
(64)
k
R = CN,
COOMe
+
R
0
0
R
4%
I
t
I
Ce(IV)
/
-
(65)
R’ 0
23
/
CN
1) 2)*
TCNE
CHO Fe(COj, (66)
Fe(CO)s References p. 303
220 Theses dealing with _in situ generation and use of tris(triphenylphosphine)Cl427 and a-carboalkoxyvinyl copper reagents Cl431 have recently
nickel
appeared. B.
Conjugate Addition
Organocuprates
continue to be the reagents of choice for conjugate of enones. Most current work centers on the development of new
alkylation reagents
and their
to the total synthesis of large molecules.
application
The new organocuprates
Li Cuz( Me) a, Li&u(Me)s and LiTCus( were studied While each show different, in their reactions with conjugated enones. solvent-dependent behavior, ii2Cua(Me)S in ether gave excellent results
with
all
enones
tested,
of added lithium studied.
and reacted
iodide
faster
or 12-crown-4
The crown ether
(2 equiv.)
than R,CuLi [144]_
on the reactions completely
MepCuLi wi th 4-methyl cycl ohexenone (con jugate (al kyl ation)
and the
Lithium iodide
enol acetate
lowered the yields
Me2CuLi, but did not completely conditions
for
reaction
in the synthesis conjugate
(eq.
67) [146].
the reaction
addition),
hexanoyl
acetoacetate
stop the reactions_
were without
of lithium
of R&uLi were
inhibited
any additive
Lithium methyl-,
(1-dimethyl aminoethyl )phenyl]cuprate
reagents
iminati
relative
to
The most efficient at al 1 [145].
acid and dehydroabietic
dimethylcuprate
of
chloride
(addi tion-el
of each of these reactions
of both podocarpic
addition
cyclohexenone
of ethyl
The effect
acid was the
to the appropriate butyl-
A key step tricyclic
and phenylC(+)-2-
were prepared
and reacted
wi tt
(67)
R’ methylcinnamate.
[147-J. thesis
transferring
R” the methyl,
butyl
or phenyl
groups
Divinyl cuprate additionstocyclopropylacrylicesterswas of (r)-eremophilone (eq. 68) Cl483. A new organocurpate
selectively usedinthes. containing
221
-+ *
l
0
(68)
0 eremophi
“Ox”“+ (MejC-CsC+-CU
lone
+
_
boEt
0SiMe3
bSiMe,
0
*
2.
(69)
Qr 0
References p. 303
222 a protected (eq.
acrolein It reacted
69).
steri c hindrance methylene
well with conjugated
in high yield addition
by free
radical
Prostaglandin
addition
(es.
70) Cl511. cyclic
jugated
The
axial,
while
Best results iodide
the menthyl
ester
addition
of phenyl,
copper
of alkyation
substrate
2.2% optical
catalyzed
Mixed cuprates
yield
yield
of
the
and
esters
cuprate
71) C1521.
with the intent
having
7.5% yield
of
cuprous
complex (eq.
was obtained
a 65% yield
Grignard
con-
stereospecifi-
has been reported.
and a mixed
and in the presence
cuprate,
of
osides
systems involving
with E-furanoacrylic
with 10% optical
mixed
but only Copper
studied.
the
of substrate
same chiral
tained
of
a variety
completely
using heterogeneous
at the site
went in high yield
produced complex mixtures.
group as the nontransferrablemoiety.
methyl ester the
occurred
than the tri-n-butylphosphine chirality
with
[150].
of a cyclopropyl
With hex-2-enopyrano-4-ul
alkylation
of organocuprates
of inducing phenethyl
organocuprates
hex-1-enopyran-3-uloses
were obtained
rather
The reaction
The reaction
by
enones,
olefin
using the alkylation
were studied.
hex-3-enopyranosid-2-uloses tally
of
as
while allylic
to conjugated
HBr to the tenninal
as a key step.
reactions
lactones
fell
w-Bromoketones were prepared
Fza was synthesized
ketone by a mixed cuprate
studied
an approach to C-
were unreactive
divinylcuprate of
reactions
but the yield
offered
halides
[149].
of lithium
and its
enones,
This chemistry
Vinyl and alkyl
lactones.
the conjugate
group was synthesized
increased .
halides-alkylated followed
alkyl
of
added
Using
a chiral
a
of conjugate [1537.
lithium
conjugate
addition
continued
to
With the chloride
and
was ob-
[154].
reactions type
also
[RCuMe3lgX,
be extensively
where R was allyl,
OSi-tGuMe, 1 R,SiO--
+
C3H7C=C-Cu &sH,,
OSi-tBuMep
(70)
/
HllCs
+ %
OSiR, 88%
+
*
PG F,r
223
4 -2
MeLi BuaPCuI
+
OEt
R = trityl (71) OR
Me LiMe?Cu
CHz=CH-CHzCHz-, transfer and
the
the
tion
containing
substrate
was
the
CHz=CH- (CHz)s-
and group
was
main
the
reacted
with
3-methylcyclohexenone,
(75%)
product
methylation
A variety
[155].
and organocuprates to Z-furanacrolein has t-butylmagnesium
salts,
high and
halides,
while
1,4
with
concentration LiMe2Cu
addition
to 1,4
addition
by running
the
benzyl from
(69%)
reactions
methyl
to transfer 40-50X
yield
Trisubstituted addition alkynes
with
the
alkyl
(alkyl
low
favored Copper
(68%)
than
and
ally1 allyla-
tetrasubstituted
and
were
substrates
copper(I)
were
group,
produced
and
bromide
or
was true.
addition.
Both
using
vinyl
A
MeMgI/CuI
conjugate
slow
(41%), "ate"
producing
n-butyl,
also
1,2
iodide,
i-butyl,
by the
to conjugated
catalyzed
isopropyl
reverse
catalyzed
Copper
stereospecifically
reagents,
the
and
(80%),
p reduced
With
addition
to good
yield
addition
of
In this fashion the following groups
[157].
(not methyl)
cuprates,
iodide
rather
was achieved in fair
temperature
n-pentyl
= n-propyl,
olefins
2,3-butadien-l-01
p. 303
(54%),
trialkylborates
by Grignard
copper(I)
References
at
cyclohexyl
of vinyl
Allenic The
Ph
and
R was
by using
favored
C156].
to suppress polymerization.
were introduced:
to primarily
when
of tri-
made.
halide
reagent
of Grignard reagents to ethylacrylate
acrylate
been
was
benzylmagnesium
of Grignard
led
enones
However,
ii comparison of 1,2 and 1,4 addi-tion of Grignards
enones were examined.
iodide
conjugated
unsaturation.
reactive
Shexenyl
reacted
with
synthesized catalyzed
enones
(eq.
towards
of alkyl-
trans
RCHzCH=CHCHzOH
prepared
ethylpropiolate
E alkylacrylates n-hexyl)
copper
reaction
(73L),
complexes,
72)
by conjugate alkylation
complexes.
phenylmagnesium [160].
of
[159].
organocopper and
in
C1581.
Conjugated
halides
: '
R3MgBr
f R’+
RlCH=CH-C-R2
H
Rb
RQ R3 = Et,
n-hex,
R4 = n-hex,
enone
=
-f
R1
R2
0
nBu
Et
p$Ph,
pf12
69
ms
+ (low
CH2=C=C
yield)
,COOEt ‘H
(73)
RIR’C=C=CHI 70%
OAc R3p_CuLi
-I-
R1R2kCSH
-+
H
R~R+C=C=C’
R1R2-C-CXH R3’
‘cu
‘R3
(i
I
I 0
&,
R4
45-60%
R’R2C-CXH ;HzOMe 75%
225 allenic
esters
underwent 1,4 alkylation
was reacted
with an allylic
73) Cl613.
Propargylic
allenic
cuprates,
(eq_ 74)[162]. enolate
halide,
acetates other
formed by conjugate
surprising
reacted
which were further Several
observation
cases
addition
that
alkylation of the enone (the less ted cyclopentanones were prepared. [163].
dialkylated
The conjugate
followed
by treatment
offurtherreaction
have been reported.
Based on the led to cis
stable product) several cis 2,3 dialkylaB-Vinyl groups did not have this effect,
of lithium
dimethylcuprate
Finally,
to produce
of the copper
addition
of the enolate
which (eq.
with a number of reagents
with vinyl
with two equivalents C165].
with organocuprates
treated
were obtained
3,3,5,5-tetramethylcyclohexanone addition
lavandulol
species
rea:snt) led to the production hexanone in good yield [164]. P-en-l-one
ultimately
!3-phenyl groups on cyclopentenones
a
and trans
to produce a copper enolate,
producing
cuprates
(eq.
75)
to cyclohexenone
with Me2N=CH‘CFsCOO- (a new Mannich
cycl oof B-methyl, a-dimethylaminomethyl Treatment of 3-chloro-5,5-dimethylcyclo-hexof lithium
dimethyl
in 76% yield
dimethylcyclohexane
cuprate
produced
by combined alkylation-conjugate dicarboxylates
were obtained This
by the addition of lithium dimethylcuprate to methyl crotonate.
1) Me7CuLi L 2 ) MeI
(75)
but 0
0 1) (0,CuLi 2) -or-
_-
(ia
less than 3% cis
69% // Me
0
COOMe
H;:
A
OMe
+
RR' CuLi
F;
(76)
ti dOOMe
49:: References
p. 303
product
arose
from a sequence
of
1,4
additions
and a final
cyclization
(eq.
76)[1667. A variety
of other
Treatment
of zinc
produced
a complex
in THF at O” for
have been used to effect conjugate additions.
metals
halide
with
[IRsZnLil
thirty
three
which
minutes
to copper.
These were then 77)
(eq.
Cl681.
1,4
alkylated
[167].
from al kynes by hydrozirconation
enones
equivalents
coupled
cyclohexanone
Vinyl copper
followed
Similar
of organolithium
to dienes
were prepared alkenyl
or added 1,4
was effected
CuCl
in 94% yield
species
by stereospecific
chemistry
reagent
transfer
to conjugated
by transfer
of the
l 3’ \ -
[\
cu
+CaC=H
90%
i-
-
(7
\
Cp,ZrHCl
Cp,ZrC
3)
Hz0
\
0 73%
RI
R2
I)
Cp?ZrHCl
R2CXR1
2) H
/ T
R4 3
Ni
(acac),
0
>
HsO’
(Zr) (71
R1 = t-Bu, R2 = H,
Me,
n-hex, Et
Et,
CsHI,CH201\Omonosubst. disubst.
Substrate
alkynes al kynes
50-95% yields 6-10% yields
227
vinyl
group to nickel
(eq.
78) [169].
The conjugate
addition
of
butyl-
magnesium bromide to (Z)-(ZR,3S)-6-benzylidine-3,4-dimethyl-5,7-dioxo-Zphenyl perhydro-1,4-oxazepi hydrolysis
99% enantiomerical Arylpailadium
complexes,
in a similar
promoted 6-arylation
prepared
chloride,
fol 1owed by
of 3-phenylheptanoic
by the ortho
enones to replace
The a-alkylpalladium
amine reacted
by nickel
gave a 92% yield
acid
ly pure [170].
added 1.4 to conjugated [171].
ne catalyzed
and decarboxylation
complexes fashion
of conjugated
(eq.
palladation
the palladium
resulting
of benzylamines
by the enone (es.
from methoxylation
80) 11727.
enones by aryl
Palladium(O) halides
(eq.
79)
of allyl-
catalysts 81) C1737.
Both E-bromo and 3-bromothiophene reacted with ally1 alcohols in the presence of palladium acetate catalysts to produce aldehydes or ketones in a formal s-alkylation
of ally1
alcchol
(eq.
82) Cl74,
1751.
\ K?
(79)
0
-
2
92%
+,
7
References
9
0
p_ 303
fai1s
,
Tph,
%
a or a alkylation
also
work
slows reaction
228
NMe,
Me0 Me + PdClz
+ MeOH
0 XS EtsN rfx PhH
+
+
Me2
(80)
(81) COOMe
67% COOH
JoH
7OH PhBr
+
f
OH
,
60-981
yield
0 also
work:
/
ToMe
t
Titanium to conjugated
an angular
BreCHO,
tetrachloride
ally1
reaction
carbene
anions
group
also
promoted
The
enones.
tetracarbonilferrates The
BraCN,
method
in a fused reacted
went
added
with
1,4
the
BraSMe,
conjugate
was used decalin
with
for
system
conjugated
acrylonitrile
to d,B-unsaturated
(eq.
addition
the
direct
(eq.
enones 84)
83)
ieq.
1,4-diketones.
Finally, 85)
of
Alkyl
[176].
to give
C1771.
compounds
of allylsilanes
introduction
[178].
chromium
229 R Br
Pd(OAc)? cat. HMPA 100%
+ 9 OH
.
+ dH
+H
0 40%
RX
+
yield
Na*Fe(CO)&
-+
5:4
R E(CO)L,
+
mixture
' Tf
R = n-Bu,
References
n-hex,
p. 303
Et
0
-
RC@T
0
230
/L
/ A
COOEt (92%),
m
COOEt (82%),
A
COO-t-Bu (83%),
I\/\/\/*
/
-COOEt
(84)
/ A
CN (95%),
(61%),
CN (92%)
-
\
1) base
(CO)&-
2) ’ ?f
-+
(CO),Cr
(85)
x
0
0 Cl %
Acylation Phase transfer C.
catalysis in carbonylations of organic halides has been to the corresdeveloped by two groups. Benzyl bromides were carbonylated ponding phenylacetic acids by reacting the halide, carbon monoxide and a catalytic amount of Coz(CO)s in a benzene-5E NaOHsystem, using triethylWith o-methyl benwl benzylammonium chloride as the phase transfer catalyst. bromide,
a double
in addition
carbon monoxide insertion
to the normal prcducts
chloride,
carbon monoxide,
[179].
occurred A similar
to give ArCH(COCOOH)CHzA system using benzyl
sodium tetracarbonylcobaltate
as catalyst,
with a
diphenyl ether-aqueous sodium hydroxide solvent system produced phenylacetic acids in 85% yield C180]. Iodobenzene was converted to methylbenzoate by treatment
with carbon monoxide in the presence
palladium
or nickel
Cl-is
alkyl
in alcohol
iodides
in methanol-diethylamine were converted
86) [183]. acyiiron
Allenes complexes
Cyclic and polycyclic
solvent
ClSl].
to the corresponding
with carbon monoxide at 200-250a
zeo? i te catalyst C1821. o-bis(bromoinethyl)benzene
of tetrakis(triphenylphosphine Straight
esters
in the presence
of a rhodium-NaX
2-Indanone was produced in 80% yieid with sodium tetracarbonyl cobaltate
were acylated
to produce u,B-unsaturated
via a n-heterobutadiene aliphatic
by treating in THF (eq. ketones with
iron complex (eq.
compounds were synthesized
chain
by treatment
87) [184].
by the insertion
231 of olefins ability Many
and
carbon
to chelate,
products
monoxide and
were
into
terminal
often
nickel-carbon
vinyl
obtained
groups
(eq.
88)
bonds.
were
[185].
Strained for
Grignard
reagents
with aryl halides and carbon monoxide in the presence
reacted nickel
dihalide
alcohols
complexes
Cl867.
of organic
halides
ences)
with
and
appeared
to produce
Reviews with
the
[187,
dealing carbon
mixtures
with
metal
olefins
monoxide,
carbonylation
of ketones
transition
of organic
olefins,
required
and
and
reaction.
of dialkyltertiary
catalyzed
reactions
acetylenes
halides
(44 refer-
(70 references)
have
1881.
NaCo(CO),,
+
x
(86) 80%
NazFe(CO)k
f
RX
f
-J
CH2=C=CH2
t<, \
R
30-60:; R = Et,
n-Pr,
n-Bu,
n-hexyl
(87) also 0
NaZFe(CO)I,
+
BrCH21 Y,CH=C=CH/
Dialkynylmerclry
compounds
reacted
at room temperaturr in the presence dialkylmaleates the
Cl :9].
treatment
nickel
(el.
stereochemistry
rhodium
catalysts
hydride
and
olefin
for both
the
production
maintained
aldehydes
References
C1927.
p. 303
was
complex,
palladium(I1)
arylmercuric
and
catalysts
diarylketones
hydroformylation
examined.
groups.
isomerization
of a rhodium
monoxide
were
halides
alcohols
to form
synthesized
in the
by
presence
of olefins was the subject of extensive
of the was
fonnyl
carbon
of
89)[190].
The hydroformjlation The
with
with
of
Unsymmetrical
of a .yliodides
carbonyl
/ ?Y
-f
The studied
Both
mechanism [191-j.
triphenylphosphite
of normal
catalyst During
the
course
and
of both A new
from
cis
the
system
acetate
a-olefins.
was
The
formation
reaction
cobalt
addition
and of
the
hydroformylation
catalyst
sodium
promoted
of this
with
promoted
and
aldehydes
activity
of olefins
metals
research.
and
consisting developed
sodium
acetate
of normal
traces
of oxygen
in
I
232
-Cl
+
CO f
Hz0
+
Ni cat.
-
(88)
Very reactive
W,
5+JE+
,
0
,
45 0
Unreactive
PmR
’ , 0,
0
,
0
R*I +RyJ-Hgx O Nio,
P-2 ’
,
l
\
(89)
R'
R
60-90X
R = H, 4-Me, 4-NH2 R' = H, 4-Me, 4-U
the synthesis catalyst.
gas oxidized
the phosphite
to (PhsO)sP=O, deactivating
the
toluene
Scrubbing of the synthesis gas with triisobutylaluminum in suppressed this oxidation 093-J. The hydroformylation of deuteratec
o?efins
with cobalt
catalysts
and the data obtained olefin
Ti-complex 0941.
at high carbon monoxide pressure
were consistent The percentage
with initial conversions
formation
was studied, of a catalyst-
in ethylene
hydroformy-
233
lation
over
Rit(C0)Cl[P(CsH~R)slz
frequencies
of
the
hydroformylation phosphine
correlated
phosphorous-rhodium
of
ethylene
adsorbed
over
on y alumina
step
c1961.
Cyclic
to give
dienes
depending
on ring
underwent
?arger
ring
compounds
lation
(eq.
9O)C1971.
hydrofonnylation ditions
the
moderate
of
1-pentene
clusters
rather
as a rate with
to
give
intact,
acetamono-
dialdehydes
were used
for terminal hydroformulation
the
propionalde-
than a second
and 500-1200 remain
of
favored
at
to
loss
a catalyst
rings
clusters
130°,
triphenyl-
bis
hydrofonnylation
carbonyl
were claimed
selectivity
Cl981.
reduction
of
carbonyl
with
as Small
vibrational
The kinetics
Rh(I)H(CO)(PPhs)z
underwent
size.
Cobalt
infrared
I)
were consistent
tocarbonylbis(triphenylphosphine)rhodium(I) dialdehydes,
the
T;-allylrhodium(
hyde from Rh(III)Hz(acyl)(CO)(PPh~)2 limiting
with
bond C1951.
to
psi. yields
and
while
hydroformycatalyze
the
Under these
con-
were high,
and
was observed (eq. 91)
The catalytic activity of rhodium(I) complexes as hydroformylation
/ -t 0
CO
\
+
Hz
+
cat.
Rh(I)
dH0 catalysts
depended
the
phosphines
led
to
of
state
of
both
phosphines
to
polymer
bound phosphine
or
at
two
most
of
Substitution
coordination. by one
phosphine
of
a fi
of or
one
of
trisphosphine
complexes of higher activity than the parent complex, while
bridged
substitution
on the
RhH(CO)z(PPhs)z
polymer
gave
ligands
bound
complexes
led
to
phosphine
of
trans
groups
lower
square are
Compl exati on
activity. planarcomplexes
coordinated
in
[199].
which
A
CHO /\/+
+
Hz
+
CO +
cat.
-+
wCHo
+
(91)
cat.
=
catalyst consisting
of
60-80”
psig
References
and 800-1500 p. 303
(PhsP)zPtClz-SnC12 Hz/CO to
give
hydroformylated 85-903
yields
of
e olefins aldehyde
at with
234 85-93’6 selectivity
for
was hydroformylated optically
active
of catalyst
straight
chain aldehydes
aldehyde
C2017.
The product
in the hydroformylationofethyl
methyl crotonate was studied.
Startinq
to phenyl or cyclohexyl
phosphine
[203].
using a palladium olefins
and related
hydroformylation
in high yield
stereospecificaily
With R equal
was observed,
while
tertiary
phosphines
and
in the rhodium carbonyl-tertiary
of 1,3
dienes
to dialdehydes
was asymmetrically catalyst C2041. were obtained carbonylation
under mild conditions
with (Ph3P)2Ni(Ph)Br
of Hz/CO
or RhzClz( CO), alone gave
has been reviewed
Linear a,s-unsaturated esters and (MesPPh)2PdC1z-SnC12 catalyzed proceeded
the catalyst_
80% a acylation
as cocatalysts
reactions
methyl methacrylate,
The use of aliphatic
a-Methylstyrene dichloride-(-)DIOP
as a function
diphosphines of various chain
triphenylphosphines
C2027.
phospholanes
catalyzed
vestigated
and n = 2-4,
distribution
acrylate,
with RhzC12(C0)4,
diphosphines,
very low a-selectivity P-substituted
a-Deuteriostyrene
at 150“ and 100 atmospheres
and methyl tiglate
length (R,P(CHz)n PRz) were added to generate
use of longer
[2007.
in the presence of a chiral rhodium catalyst to give
was in-
hydrocarboxylated Hydrocarboxylation
of
[205]. by the (ArzP)zPdClz-SnClz The reaction of 1-alkynes.
[I2061.
2-Butyne reacted
in methanol to give
a vinyl
complex
which upon carbonylation produced 98% a-a,&dimethylcinnamate c2071. Treatment of acetylene-hexacarbonyl dicobalt complexes with alkenes or cycloalkenes were obtained strates reviewed
for
produced cyclohexenones. (eq.
92) [208].
the synthesis
(258 references)
With unsymmetrical al kynes,
Carbon monoxide addition
of quinones,
acrylic
mixtures
to acetylenic
and succinic
acids
sub-
has been
[209].
(92)
30-60% R = H, Me R’ = H, Me, Ph
Several
new olefin
carbonylations
monoolefins were aminoacylated,
have been developed.
Simple terminal
by treatment with diethylamine followed by
carbon monoxide in the presence of palladium(I1) chloride, to produce 8aminoacid derivatives after oxidative cleavage (eq. 93) C210].
Transition
metal catalyzed carbonylation of olefins was reviewed (289 references) [211] Isoprene was acylated to produce 4-methyl-3-pentenoate
esters by treatment
235
with carbon monoxide in the presence catalyst
of a palladium
acetate-triphenylphosphine
system.
converted
Cyclic olefins -No isoprene dimers were formed f212]. to exocyclic trial kylsi lenol ethers by treatment with carbon
monoxide,
trialkylsilane
, and dicobalt
octacarbonyl
(eq.
R -
+
PdC12(CHzCN)z +
R2’NH +
CO
were
94) [213].
R2’
N
‘Pd’
* %
Cl ‘NHR2 ’
0
(93) 1) Et-?, -78O 2) BH 0
60-70% BH = CH,OH, NH,, EtzNH
+
n = 3
48%
n=4
71X
n = 5
74%
n=6
69% Oxetane,
CO +
COT(CO)*
THF and epoxycyclohexane
methyldiethylsilane carbonyl
HSiRs
to give
(94)
were cleaved
by treatment
and carbon monoxide in the presence
rrith
of dicobalt
octa-
Et2MeSiO(CH2),CH0 and Z-(methyldiethylsiloxy)cyclohexane
ether carboxaldehyde C2147. Vinyl silanes reacted with dichloromethylmethyl in the presence of titanium tetrachloride to produce conjugated aldehydes w-unsaturated alkylsilanes were acylated by in good yield (eq. 95) [215]. treatment
with titanium
Metal oxides
tetrachloride
the acylation
at 150”.
Anisole,
halobenzenes
using FezOa
in high yield
by substituted of a separate References
p. 303
(eq.
96) [216].
such as Fe203 ZnO, Moos, (NH4)sMo7,0zG~4H20 and Na2GI0,
catalyzed tion
and acid halides
of isomeric
xylenes
with
and alkylbenzenes C2171.
benzoic acid chlorides report C2187. Pyridine
benzoyl acylated
The benzoyl ation
chloride
in 10 hr
in the four
posi-
of ha1obenzenes
catalyzed by Fe2(S0,)s was the subject was treated with phenyllithium followed
236 Rl
R2 +
M H
Cl,CHOCH,
(95
SiMes
H
CHO 72-85'5
R1 = n-pentyl,
n-Bu,
Ph,
n-propyl
R1 = H, n-propyl
(961 0
RM
_,_
It
R&j
O-28%
by iron
pentacarbonyl
not
normally
The
Gatterman
trichloride
to give
accessible Koch and
38-63:;
direct
acylation
to electrophilic
reaction
Cu(PPhs)Cl.
of toluene
in the
substitution was
promoted
Triphenylphosp1,1ne
6 position, (eq.
97)
by mixtures
inhibited
this
a site
[219]. of aluminum reaction. CHO
Ph 73%
COOH C ii
(’ Ph
t?
-R
24-323
23'i OC1 -I-
ti
COCl
fe(CO), (98)
(CO)3Fe
(99)
m OtBu
/
1
+
f
Fe(CO),
(100) cage dimer 14%
References
p. 303
Bu,O
+
linear trimer ketone 78%
238 The iron tricarbonyl
complex of the acid chloride of cyclobutadiene
dicarboxylate acylated 4,4'-dimethylbiphenyl
(eq.
98) C2217.
bony1 and crotyl
The reaction chloride
c2221.
primarily
acylated
of endo dicyclopentadiene
in acetone-water
Iron pentacarbonyl
to give a polycyclic complex
reacted
dimers (eq.
with nickel
gave a tetracyclic
with 7-t-butoxynorbornene
100) C2231.
Norbornadiene
car-
acid
(eq.
99)
to give itself reacted
with iron pentacarbonyl and alkynes to give polycyclic ketones (eq. 101)
Lactones
t224J.
were formed by the photolysis of unsaturated epoxides in
the presence
ofironpentacarbonyl
from similar
treatment
Finally, cyclic
an unusual series olefin
iodide
developed
though maximumactivity of these metals. examined [2287.
(eq.
carbonylation
No significant
in detail.
promoted reaction
102) c2251.
ketones
resulted
103) [226-J.
and rearrangements
of iron
of methanol to acetic
acid was
was noted between the methyl
by rhodium or iridium
was achieved
under different
Iridium was the best catalyst Ketone solvents
(eq.
104) C2271.
difference
catalyzed
Cyclic
cyclopropanes
of carbonyl&tions
complexes was reported
The recently studied
(eq.
of unsaturated
complexes,
conditions
of all
such as acetophenone
for
aleach
the platinum metals and benzophenone
600Me(COOEt)(Ph)
(101) +
HCK-COOR
-
COOR 15%
kept both the activity elevated conditions
temperatures involving
was found to also effectively
and selectivity C2291.
of this
In a departure
methyl iodide
as a promotor,
promote the carbonylation
than methyl iodide
12307.
ated compounds has been reviewed
reaction
high,
from the standard
reaction
pentachlorobenzene
of methanol,
The carbonylation
(103 references)
even at
L-2311.
although
thiol less
of saturated
oxygen
Arnines were car-
239
0
d/
m 0
(102)
\
70%
O
\ Qr 0
(103) (no yield
bonylatec! carbonyl
to formamides by treatment via iron
a-diketones and an alkyl
with carbon monoxide and iron penta-
carbamoyl complexes
by sequential iodide
(eq.
treatment 105) [233].
[232].
and mechanistic
aspects
Acetals
were converted
with butyllithium. Transition
for organic synthesis has been reviewed
thetic
given)
metal carbonyl s as reagents
(81 references)
of inorganic
insertion
C2341, as has synreactions
Reviews on carbonylation
reactions
C2361, and the chemistry
of potassium tetracarbonylhydridoferrate
references)
References
under mild conditions
C235-J.
(53 references) (17
(I2371 have appeared.
Decarbonylation the topic
to
iron pentacarbonyl
of a thesis
p. 303
of racemic aldehydes C2381.
with chiral
Decarbonylation
reactions
rhodium complexes using transition
was
240
(104)
0
43 R = Ph, Et, n-Pr, Me R' = Me, Et
metal compounds has been reviewed
(144
references)
C2391.
The stoichiometril
decarbonylation of (S)-(+)-PhCHDCOCl with tris(triphenylphosphine)rhodium(I) gave (S)-(+)-PhCHDCl in 20-27X scrambling labelled also
between chloride.
examined.
substrate,
overall product
stereospecificity. and catalyst
The decarbonylation The results
favor
Rapid
was detected
halogen by using
of C6DsCD2CH2COC1 to styrene was
a mechanism
in which
a rapid
preequili-
brium between acyl and al4ylrhodium complexes is followed by a concerted cis
24 elimination
of
rhodium
hydride
[240-j.
Substituted
(styracins) containing hydroxy substituents
cinnamyl
in the aromatic rings decarboxy-
late8 .cO 1,5- ~~a~~-l,Pf-p~rrtacti~rres crpun tredtmenc pal 1 adium catalysts 0.
cinnamates
with
platinum
and
L2417.
Oligomerization
The cationic complex produced by treatment of bis(triphenylphosphine)pentachlorophenyl(chloro)nickel(II)
with silver perchlorate catalyzed the
dimerization of ethylene in bromobenzene amount of
added
dimerized
by Ziegler-type
palladium(I1) in the for
triphenylphosphine
the
of
aluminum halides
of
of
effects
isomerization
the
arsine
propylene
phosphine
highest
based
ligands [243].
activity
of
chloride
selectivity
for
the
Catalytic
nature
complex
having
the
of
highest
alkyl-
the
ligands
catalyst,
2-methyl-2-pentene
systems
halides,
or stilbene
the
ligand.
strongly
with
triphenyl-
isomerization
[244].
activity
Brominated
polystyrene was treated with (tetrakis)triphenylphosphinenickel(O) resin bound nickel( II) boron
trifluoride
efficient
aryl complexes.
etherate
catalyst
solvent
although
C245;.
Zerovalent
for the
the
nickel
dimerization
of
amount of
water
propene.
N-hexane
was completely
complexes
such
insoluble
and [(ptoly-O)sPJzNi(CHzCHz)
or trifluoroacetic
acid,
produced
best
solvent
[(EtO)3PlnNi,
when treated
catalysts
an
was the
in this
as (PhaP)kYi,
(Ph,P)zNi(CHzCHz),
were effective
to form
Treatment of these resins with
and a catalytic
catalyst
was
and
and alkylaluminums
on n-allylnickel to
Propylene
nickel(I1)
base
by arsine
A catalytic
C2421.
planar
ligands
were sensitive
ligands
and diethylaluminum
and the
Schiffs
containing
and ligands
Replacement
activity
from square
chelating
phosphorus
dimerization
enhanced
catalysts
complexes,
presence
at O” and 1 atm.
for
with
olefin
sulfuric
dimerization.
The catalytically active species was thought to be a nickel hydride C2461. Polynuclear palladium(I1) complexes were implicated as the active catalysts in the
oxidative
was involved tive
dimerization
of styrene
in the rate limiting step 12471.
dimerization
of
for a-methylstyrene,
olefins
in the
presence
C2501.
2500 was produced
of
was completely was studied cyclooctadiene The starting ally1
saturated of
by treating nickel, material
isomerization
Referencesp. 303
by treatment
pentacarbonyl
The mechanism
the
oxida-
were studied
C248, 2493.
Polycyclohexane
cyclohexene
and ethylaluminum and the
rings
the nickel(O)
with
triphenylphosphine rapidly
isomerized through
molecular
dichloride.
were retained
catalyzed
of
a catalyst
u-complexes
from
The polymer of
1,3-butadiene with
in benzene to the
weight
prepared
C2517.
dimerization
cis,cis-1,4-dideuterio-1,3-butadiene
proceeding
of
palladium(I1)
and isomerization polymerization of unsaturated
hydrocarbons has been reviewed chlororhenium
The kinetics of
stryene and l,l-diphenylethylene
Hydrodehydropolymerization
Pdj(Ohc),
to 1,4_diphenylbutadiene.
bis-
at room temperature.
trans,trans 12527.
diene Mixtures
via
an
of
di-
242 methyloctatriene isoprene
isomers were formed by the tail
over phosphine pailadium(0)
CO2 assisted
to tail
complexes
dimerization
in the presence
of
of CO2.
The
in the formation of the catalytically active species c2537.
The selective
dimerization
by catalysts
prepared
metal halides
of butadiene
to 4-vinylcyclohexene
by the metathetical
reaction
was effected
of NaFe(C013NO ivith
such as CM(NO)aXlz where M was Fe and Co, and X was Cl,
Br
and I C2541. A proper amount of water was found to enhance the catalytic activity of sodium borohydride-amine-bisphosphine nickel dihalide catalyst systemsforthe
dienes
with n-propylamine,
attacked
The principle
dimerizationofisoprene.
monoolefins
and cyclic
ones with pyridine
such as styrene,
propene,
Me2C=NMeat the carbon atom of highest coefficient nickel
in the lowest
catalysts
C2561.
reactions catalyzed references) [257]. prepared selective
long life
cyclooctadiene. lifetime. catalyze
unoccupied
Oligomerizations,
A nickel catalyst
for
The catalyst
It catalyzed reduction
of olefins
value for
electron
density
polymerizations
and other
complexes havebeen
of
diolefi?
reviewed
(20
complex Ni,(CN-t-Bu)7,
and t-butylisonitrile
was an excelleni
of butadiene
cyclotrimerized of alkynes
and
in the presence
the dimerization
also
reduction
Butadiene
[2551.
orbital,
cluster-isonitrile nickel
were linear
methyl methacrylate
absolute
molecular
by homogeneous nickel
from biscyclooctadiene
products
to cis
alkynes. alkenes,
to 1,5-
but had a short but did not
12581.
The combined oligomerization-nucleophilic
M
+
attack
sequence
involving
CHsCOOH Pd(OAc);?, PPhS 1
1 //,
OAc I
OAC P,z,
OH-
RuC17_L3
i OH
I
Pd(OAcj2,
&
PPh3
(1061
1 j i-BuzAlA 2) LiAlHJ Cp2Ti Cl 4
OAc H70+
&
243 butadiene
has
presence
106)
of
to prepare
reacted
a variety
with
triphenylphosphine
Butadiene
c2591.
presence
used
Butadiene
compounds. the
been
reacted
acetic to
with
of
acid
give
unsaturated
a-ether
esters
and
u-hydroxy
107)
polyolefinic acetate
in
act-1-en-3-01
acids and
(eq.
palladium
ultimately
of bis(acetylacetonate)palladium(II)
produce
interesting
or esters
(eq.
in the
triphenylphosphine
C2601.
The
queen
bee
to sub-
R M
+
Pd(acac)? 2oo, PPhs
HO-iH-COOR'
’
(107)
A/\
COOR
R = H, Me R' = n-Bu,
Et
/-,
COOEt
Pd(OAc)_, PPhs
•I- CH,(COOEt)z
COOEt
95x
PdCl?
CuCl,
l
+COOEt
H?
02 COOEt
67%
+cooEt
(108) COOEt
COOEt 47%
References
p. 303
dil.
KOH ;Lw
\ queen
bee
substance
COOH
244
-
+
CH3N02
Pd(OAc);, PPh,
l
/
/ /
--++gy-+ NO2
87%
(109) OH
Ho-OL/O 86%
rii -L
1) Cr?O,, acetone 21 Na, xylene
L
-
60%
92% cis
civetone
stance
was synthesfzed
in
presence
the
of
palladium
t.2613.
cis
Civetone
acetate
(eq.
109)
carbon
monoxide
by the
reaction acetate
was prepared
C2621,
while
and t-butanol
triphenylphosphine
(eq.
/w,
f
butadiene
and diethyl
and triphenylphosphine from
royal in
110)
of
the
nitromethane,
jelly
acid
presence
(eq.
butadiene
was prepared of
pal ladi
malonate 108) and palladium from
um acetate
butadiene, and
C2631.
CO
+
Pd(OAc), PPh3
t-BuOH
CO2(CO)R
/e
MeOH
COOtBu 90%
(110) COOtBu
/
MeO,CW 62%
hydrolys
i s
\
HOOCn./\/\/\/C
OOH
80%
royal
Ni(acac)
00
+
,/
+
COD
f
+
jelly
AlEt,
CF,COOH
acid
+
(Ar0)3P
+
catalyst
;“;;1,‘& (Ill)
t 64%
33% 62%
Use of
Bu,P
+
984
m
n Nwo
References
p_ 303
-P!
246 Reduced morpholine butene
nickel
species
to give
mixtures
or octadiene
butadiene amines
and
(eq.
trisubstituted
(eq.
Ill)
palladium
piperdines
reaction
from
to give
+
and
RaP
+
amines
octadienyl
system
urotropine
with
reacted
with
substituted
produced
EtaAl
with
at nitrogen
Primary
catalyst
butadiene
?-'(acac)
of butadiene
substituted
[264].
species
A similar
[265].
the
of morpholines
groups
reduced
112)
cata?yrsd
1,2,3-
(eq.
113)
[266].
Catalyst
+
NHCH2Ph f
-i- e
PhCH2NHz
CFqCOOH
catalyst
~
-
-JW
(112) +
I/\
+
‘-
(-
+
NHPh
[Pd(acac)
)2NCH2Ph
-AraP-EtsAll
+
urotropin -f
(113)
Hydrazones
react
at nitrogen
with
in the presence of a
butadiene
palladium(O) catalyst, while related nickel catalysts cause reaction at the hydrazone carbon (eq. 114) mixed
oligomerization
presence The
of morpholine
polymerization
C267,
268].
The
product
of N-benzylidenepropylamine was
and
dependent
distribution with
on morpholine
copolymerization
of
of the
butadiene
concentration
butadiene
has
been
in the [269].
reviewed
C2701. Metal a very
catalyzed
useful
paration
cyclotrimerization
approach
of benzocyclobutanes,
cyclooligomerization (eq.
115)
chemistry
to polycyclic
C271]. was
used
indanes
of a,w-diynes An
absolutely
to synthesize
of alkynes materials. and
with
elegant the
has The
tetralines
substituted intramolecular
steroid
skeleton
been
full via
developed
paper cobalt
acetylenes version (eq.
116)
into
on precatalyze\: has
appeared
of this C2721.
247 Transition been
metal
reviewed
catalyzed
acetylene
cyclizations
in organic
synthesis
has
C2733.
2
MeNH
L,Pd
'N
'm+
l
RI
R2
/ W-N
I Me
86%
<
R’
R’ = H, Me (114)
~2 = Me, Et
‘-
+
MeNH,
R’ N
(CoD!7Ni
+
-R’ Rl Rl
N=NMe
t
60:40
mixture
=-RI Z-R -
2
f
40-60X
Ill I
R"
cpco(co)q
+ (R3 or R4 must
be -SiMe3)
(115)
n = 3-5 R's
= SiMe,,
References
p- 303
COOMe,
H, Ph,
hexyl
Me2SiCrCSiMel CpCo(CO),
(116)
estra-1,3,5(10)-trien-17-one
Ynamines underwent cycjotrimerization 1,3,4_triaminobenzenes of
nickel
of
3-hexyne
bromide
(eq.
bromide with
117) [274].
A catalyst
mesitylmagnesium
to hexaethylbenzene
complex
[2757.
using a nickel bromide
or
dimerized
complex which, ketone
upon oxidation
(eq.
by treatment
to
nickel (E)-(3S,7S)-3,7-
1,3,5-tris[(S)-1-methylpropyllbenzene
tetrachloride, depending on
condi ii ons . No racemization was observed [276]. dimerized upon treatment with palladium chloride gave a cyclic
to give
cyclotrimerization
via a tetraethylcyclobutadienyl
when treated with triisobutylaluminum-titanium
palladium
prepared
catalyzed
(S)-3-Methyl-1-pentyne
dimethyl-4-methylenenon-5-ene
catalyst
Phenylmesitylacetylene to give
a stable
vinyl-
with chromium trioxide-pyridine,
718) C277].
R
LsNi(C0)7, CH&N,
R-IX-NR2’
50”)
(117)
3 hr R NR2 ’
R = H,
30-50x
Me
Diynes cyclized rhodium(I) cycle
with alkynes
in the presence
to form complex polycyclic
‘(rhodiocyclopentadiene)
eq.
materials 119
[278]
of tris(triphenylphosphine via an intermediate
and eq. 120 [279].
metalla-
Chromium
carbene complexes of the type (CO)sCr=CPhR reacted with alkynes to give
chromi urn coordinated the coordination
s-naphthol s .
The naphthol
sphere of the metal (eq.
skeleton
121) [280].
was assembled in
249
PhH 48 hr, 25” ’
PdClz(PhCN)z
(1181 Ph CrOq-Py CHzClz ’ 24 hr
Ph
Aesityl 46%
R rPh I
L,RhCl i
+
R’CsCRz
--Ph
R G
0
Ph
R = H, Me, Et
The effect rhodium(I) product
I.
complexes
ligands
was studied
distributions.
phosphine i281
of phosphine
and the total
on the dimerizationofl-alkynes
in an attempt to alter
linear-to-branched
No simple correlation
between steric
yields
of the reaction
Treatment of terminal
or selectivity
by
bulk of the was discerned
alkynes with triisobutylaluminum
and nickel,
iron or manganese salts led to alkylation-dimerization (eq. 122) [282]. Cyclotrimerizationof isoprene with hexafluoro-2-butyneusing n5-indenylrhodium(bisethylene)
complex as a catalyst
1,2,3,4-tetrakis(trifluoromethyl)-l,3-hexadiene reacted
with alkynes
chloride
to give
cyclopropane References
p.
303
in the presence
codimers
gave ns-indenylrhodium
of palladium
chloride
which are 1-halo-1,3-butadienes
ring opened and oligomerized
when treated
Sisopropyl-
C2831. Styrene and lithium [284].
Vinyl-
with phosphine
250
ZPh
+
L?RhCl
R'C=CRl
~
=Ph
(120)
OH ,Th
+
(CO)sCr=C
R'CrCR'
+
(121)
'I? Cr(CO),
R 7-68X
R = Ph,
OMe
R1 = Et.
Me,
R2 = H, Me,
nickel(O) depended Propene with
Pr, Et,
Ph COOEt
complexes on the was
phosphine
to yield
phcsphine
converted
butyllithium
pol_ymerized
ether
Bu, Ph,
to
and
cuprous
polymerized
dihalide
chloride
and
in 50% yield
a nickel(O)
of products,
the
123)
1,2,2-Trimethylcyclo-
[285].
[286].
by treatment
catalysts
the
reacted
catalyst
with
magnesium
same
conditions ally1
to give
catalysis
and
oligomsrization
has
been
reviewed
by transition
of ethyl [289-J.
acrylate,
metal
by treatment was
metal
and his-
[287].
chloride,
a compound
with
(eq.
complexes
acrylonitrile
of which
4,4'-Dibromodiphenyl
with
rings with high selectivity and stereoselectivity Nuc7eophilic
composit'ion
Q-Dibromobenzene
in 90% yield.
under
trans-1,5,9,13_Tetradecatetraene monoxide
(eq.
2,3,6,7-tetramethyloct-4-yne-2,6-diene
to poly Q-phenyl nickel
a mixture
present
three
124)
cyclopentanone
[2881.
including and
trans, carbon
dimerization
crotononitrile
251 R Ni(MeSal)T
~ \
R-
30-66%
RCECH
+
(i-Bu)sAl
~
FeCl?
l
(122) 65%
Mn(acac)x
l
IBu-i 78%
/
(123)
90% yield
Cl
+
Ni(0)
of mixture
-+
(!24)
References
P. 303
252
E.
Rearrangements
The
olefin
symposium
in September,
been pub1 ished chloride
and metal and
yield
case
by suppressing
of
selectivity
ethanol
l-pentene,
butyltin
and
was
in the
Crafts
reactions
used
(1:4) The
was
and cocatalysts
tri ethyl al uminum [I2947.
subjected
such
hexachloride-tetrabutyltin of
linear
and
as the
tungsten
alkenes
by adding
hexa-
disproportionation
polymerization
of
hexachloride-tetra-
S-6-methyl-P-octene. 1-Pentene
using
not
tetraethyltin
system
were
The
did
tungsten
were metathesized
catalyst
chiral
solvent
the
to metathesis
esters
2-heptene.
from tungsten
as tetrabutyltin,
w-Olefinic
triethyl
with
benzene
catalyzed
as well
C2921.
now
hexa-
hexachloride-tetrabutylti
prepared
to disproportionate
Methyloleate
tetrachloride
A variety
with
have
tungsten
reactions
tungsten
A catalyst
symposium
from
(+)-(3S,lOS)-3,10-dimethyl-6-dodecene.
C2937.
tungsten
achieved
international
diethyltin,
in their
and Z-P-octene,
was
of this
as tetrabutyltin,
aluminum hydride
of an
prepared
studied
Z-cyclononene
catalyst
product
proceedings catalysts
C2917.
2-pentene
topic
such
Friedel
and lithium
the
were was
or esters
Z-cyclooctene
react
alkyls
was
The
Metathesis
butyllithium
High
chloride
1977.
[290].
alumfnum
ether,
reaction
metathesis
(eq.
subjected
or
using
the
125)[295].
to the
metathesis
(125) 83-93%
n = 2,
6,
n=8
X = CH,OAc
reaction
of
X = COOMe
8
with
chiral
this
activity
and
trans-4-octene such
by addition catalysts Pyridine
of
the
in the
isobutylaiuminum
1297-J.
of oxygen
pentacarbcnyl
aluminum dichloride complexes
CZ991.
catalysts
were carbene
and
homogeneous
isopropylaluminum
promoted reactions
of
upon
(l,&cyclooctadiene)tungsten
internal
activation
of
of cyclic
and
propagated
trans-3-hexene
R = Me', Ph)
dichloride
metathesis
by the
upon
gave
and
olefins oiefins
union
via
com-
activation
highly
olefins
by treatment
terminal acyclic
the
c2961.
or tungsten-germanium
Sn;
linear
of
and that
on the P-alkene
produced
tungsten-tin
metathesis
Metathesis
C3007.
presence
the metathesis
configuration,
depended
(M = Ge,
molybdenum
chain
of
dichloride
Bimetallic
showed that
resu!ts
retention
catalyst
as vC.~H~W(CO)~-MR~
for
The
with
of trans-3-heptene
tetracarbonyl
a metal
catalyst.
occurred
and selectivity
Hetathesis
plexes
same
2-alkenes
active
C2981. with
methyl
metal
carbene
by molybdenum
of an olefin
with
253 Fulvalene diene)(bis c3017.
was metathesized
with ethylene
titanium)dihydride The conductance
trichloride
as L catalyst
of the solution
to a solution
using (fulvalene)(dicyclopentato produce ethane and butadiene
resulting
of W(CO)sClz(AsPhs)z
from aclding aluminum
in dichloromethane
was much
greater than expected, and was attributed to the formation of the catalytically active species C3021.
Olefin metathesis of cis-2-pentene by zero
talent tungsten catalysts both in the homogeneous phase or supported
inorganic
on
oxides were compared. With both systems the primary function of The catalyst
the cocatalyst was to decrease electron density on tungsten.
on a solid
support
fatty
acids
nally
unsaturated
had a steric
and esters
effect
u,w-diesters
to ethylene
[303].
as a heterogeneous
by a catalyst
prepared
w-Unsaturated
and long chain inter-
using rhenium heptoxide
small amount of tetramethyltin were metathesized
on the reaction
were metathesized
on alumina plus a
catalyst
by photolysis
13041.
Al kynes
of molybdenum hexa-
The reaction was thought to carbonyl in the presence of chlorophenol. occur by a two-step mechanism involving activation of molybdenum hexacarbonyl
by the alkyne.
and subsequent
of the phenol and the transition the two-stage
mechanism [305].
by Ph2CU(CO)s was highly actions
catalysis
by the phenol.
metal separately The metathesis
on silica
of cis-Z-pentene
, probably
stereoselective
Heterogenation
gel supported initiated
because of steric
in the four-membered ring transition state c3061.
inter-
The stereo-
chemistry of the metathesis of cis-2-pentene by zero valent tungsten catalysts showed that four different metallocarbene internal
were involved,
olefins
initiation.
types of coordination
and all
which are nearly
Stereoselectivity
had about the same rate.
symmetrical,
of cis
reaction
has been reviewed
several
times [308]
and tertiary amines in the presence transition
metal complexes
Several
new olefin
to use synthetical
olefins
For dominate the
was explained
(91 references),
disproportionated
of triphenylphosphine
on the
[309], to primary
and a variety
of
of Rh, Ru, Ir or Ni [311].
isomerization Catalytic
ly .
factors
to the
coordinated to tungsten and/or the C3071. The olefin metathesis
Secondary alkyamines
(60 references).
steric
and trans
basis of the steric bulk of the ligands configuration of the metallocyclobutanes [310]
of olefin
catalysts
isomerization
have been developed and put
of 1-pentene
to e-
and
trans-2-pentene by HzRu~+(Co)~s and HRus(CO)sCsHs cluster compounds in toluene involves metal hydride addition-elimination sequences and o-alkylintermediates, also
observed
although C3121.
endocycl i c double
some suggestion
of n-ally1
type intermediates
was
Normally difficult or impossible exocyclic to
bond rearrangements
were promoted by rhodi urn trichl ori de
However, treatment of ergosterol under these conditions gave tri hydrate. a complex mixture (eq. 126)[313]'. Cycloalkenones having exocyclic double bonds underwent isomerization
References p. 303
and disproportionation
to aromatic
Systems
254
when treated with chlorocarbonylbis(triphenylphosphine)iridium [3747.
(eq. 172)
The reagent generated from bi-cyclopentadienyltitanium
dichloride
and
R
and
lithium
giving
an
Allylbenzene
/ i!l-
l
aluminum
hydride
isolable
(1261
titanium
both
R
isomerized
and
was
rearranged
to trans-6-methylstyrene
carbonyl.
Usfng
deuterated
substrates,
out,
results
while
mechanism and
were
o Olefins
C317].
Co(olefin)PPhs
sulfonamides The
product
used
in situ --
presence
H
consistent
[318].
by treatment was
formed
in good
when
was
ruled
with
were
but was
Co(N2)(PPh3)s
rearranged
with
to N-vinyl-
irradiation.
difficult
to purify
and
was
Ally1 alcohols were isomerized to aldehydes in the
C3191.
of tris(triphenylphosphine)rhodium
0
treated
pentacarbonyl
yield,
shift
a 1,2-addition-elimination
N-allylsulfonamides iron
1-octene
C315, 3167.
by hydridocobalt
a [1,3]sigmatropic
with
isomerized
with
hydrometallated
Cp,Ti(A1H,)(C,H,,CH=CH2)
complex
carbonyl
H
hydride
in
OH RCH2
R
R
L,Ir(CO)Cl 250", 1 hr *
90% and
Ph
(127)
255 trifluoroacetic
of chiral
With a chiral
acid.
aldehyde were obtained
molybdates
o.
to carbonyl
C3201.
.*henates catalyzed
(eq.
present
alcohols
The vanadate
yields
low optical
Vanadate esters,
the isomerization
compounds and a-ethylenic
number of cases were studied. efficient
diphosphine
tungstates,
of a-acetylenic
to allylic
esters
alcohols
alcohols.
A large
were particularly
128) [321].
+
160” 30 min.
NaH,VOs
76%
(128)
Unsymmetrical and ketones
via
by Claisen 1-4
rearrangement
Diallylesters
treated
with
C3231.
A variety
allylvinyl
the is
presence
Fe(I1)
1,5-hydride
substitution dienoic
complexes
solvent
(eq.
and ring cleavage
with
in 59-90X
132)
(eq.
131)
cyclohexadienes 1,2-Arene
C326-J.
when treated
little
in the
with of
of
(eq.
with [Rh(CO),Cl]2
730) to the
chl orotri
s-
expected
intra-
decomposition
Substituted
or cyclopentadienes
oxides
129)
when
a-pellandrene
the
similar
[325-J.
(eq.
rearranged
by treatment
with
for
acids
ligands
oxides
Epidioxides
observed
epoxide
to
phosphine
stilbene
followed
(PhsP)sRuClz
and 8,y-w
decomposition
epidioxide
of
by olefin
abstraction
rearranged
0.19
retarded
at 159-210°[325].
promoted
acid
oxides
of
aldehydes
ethers
to a,6-w
benzyl phenyl ketones
underwent
on the
B,y-unsaturated
to
or rhodium
molecular levopimaric
to
of 4,4’-disubstituted
triarylphosphinerhodium
arene
rearranged rearrangement
rearranged
nickel
corresponding
with
The reaction
hr at 200°.
[322].
diallylethers
regiospecific
of
1.4depending
underwent deoxygenation [327].
dl-Muscone
was
synthesized by the ferric chloride cleavage of a 1,2(bis)(trimethylsiloxyl)cyclopropane followed by al kylation of the thus formed enol acetate by lithium dimethylcuprate The photoassisted in the presence is
a 1:l
a-complex
via the population References
of
p. 303
(eq. 133) [32E1]. valence isomerizationofnorboradiene
copper(I)
salts
suggested
that
the
to auadricyclene photoactive
of diene and copper and that photoreaction of
an olefin
metal
charge
transfer
state
species
originates of
the
complex
256 CHO TO_ 0.1X
200” ~ L3RUC12
1 S& 99%
and
O-
(1291
u I
+
CHO
97%
(130)
‘---?rH + -OH
0
66-73% mixtures
The quantum
[329].
complexes single to
give
yields
CPPh3CulBH,
bonds
underwent
rearranged
bicyclo[l enantiomeric
.l.O]butane excess
of
this
reaction
were
and CMePPh2CulBH4 C3301. rearrangement
hydrocarbons
best
upon treatment
compl exed to
iron
with
Strained with
the ring iron
(eq _ 134)
derivatives
were
kinetically
by treatment
with
a rhodium(I)(DIOP)complex
resolved
copper carbon-carbon pentacarbonyl Racemi c
[331]. in
up to which
30%
257
OOMe
CRh(CO)7Cl-J? CHCl,
COOMe
(132)
[Rh(CO)>ClJT MeOH
l
Et7Zn CHzIz
88”-
H7, Pd/C
/ G?c
d,l
muscone
co
I
hv
References
p. 303
(134)
.,omerized
selectivel,
one enantiomer
leaving
the other
merized
and ring opened to 1,3-
enantiomer
CRh(C0)2C172 C3333. [4.4.2]Propellanes hexacarbonyl
intact
occur,
and 1,4-dienes
rearranged
at 125” to initially
released rearranged material
to a substituted butadiene, while Vinylcyclopropanes were epic332l. by treatment
upon treatment form a complex,
(eq. 135) C334l.
with
with molybdenum which then upon heating
For the rearrangement
to
1,3-cyclohexadiene had to be laterally fused to a strained fourChromium hexacarbonyl and tungsten hexacarbc;,yl form
membered ring _ stable
complexes
kinetics
of this
of benzene, (eq.
reaction
normally
135) C3367.
methyl shift,
which do not rearrange.
Deuterium isotope
effects
and
have been examined [335J. A Diels-Alder dimer was stabilized by coordination to iron
unstable,
Camphene rearranged
in the presence
to isobornyl
of copper(I1)
chloride
acetate
without
C3371.
>125O
l
CD I
-
a
(135)
i
Fe(CO)s
Ce(IV)
l
(136)
259 III.
Oxidation Electrophilic
of cyclohexene
epoxidation
as a heterogeneous this
system
plexes
was
as rle$COOH,
than
similar
as
of the
30-50%
yield
molybdenum 138)
excess
ligands
(eq.
and
lo-30%
complex
with
epoxidation
compounds
state
to that
PhCHMeOOH
enantiomeric
acids
(eq.
the
were epoxidized
alcohols 50%
similar
by PhMe2COOH
were
catalyzed
The reactivity
catalyst.
catalyzed
such
oxidation
of propylene
by t-butylhydroperoxide
peracetic
of ally1
and
alcohol
was
using
vanadium
[340].
optical
purity
olefins
by organic
or titanium,
and
unimportant
with nerol
by PhCMe200H
chiral were
and
more the
C3391.
in high yield and
towards com-
hydroperoxides much
catalysts
Geraniol
epoxidation
Vanadium
was
by t-butylhydroperoxide 137)
of
13381.
Vanadium
tungsten
.!um compound
the
by Mo205(Me2NCS2)2
a variety acid
PhCMe2COOH.
of mr'ybdenum, van
of
and
active initial
Allylic
and up to hydroxamic
epoxidized
the
in
chiral
(acetylacetonatoX(-)-N-alkylephedrineldioxomolybdenum
L-3411.
By carrying
+
t-BuOOH
out molybdenum
+
VO(acac),
and
vanadium
catalyzed
0
+
H
,AMe
Mev-*/'1, Me
*
“C~NR~H ke
R = Me, Ph, 2,6-xylyl
[
p&h
gave
best
optical
yield
(l”)
OH +
PhCMezOOH +
-+
R7B1/-o” (138 R’
References
p. 303
epoxidation
of
that
hydroperoxide
intact
olefins
by hydroperoxides
in H,‘aO,
was present
in the
epoxidation of olefins by hydroperoxides
it
active
was demonstrated complex
The
C342J.
using molybdenum(V)
complexes
with ligands such as ethylene glycol, lactic acid and amygdalic acid in homogeneous
systems,
as well
as heterogenized
catalysts
exchange reactions of Na2[Mo204(0X!2(H20)~.3H20 Oxovanadium(IV) resin
was studied C3437.
compounds were incorporated on a sulfonic acid ion
and used as catalyst
for
the
reaction
than did
comparable
indicated
that
homogeneous
the mechanism
epoxidation
of
the
exchange
of t-butylhydroperoxide
This epoxidation was much more selective
olefins.
by ion‘
prepared
with
and went in higher
reactions.
heterogeneous
Kinetic
reaction
yields
studies
was similar
to
The same vanadium compounds were incor-
that of the homogeneous case C3441.
porated into several insoluble polymers containing ligand groups such as acetylacetonate,
ethylendiamine
the epoxidation of
the
of
sodium molybdate
peroxide
was zero
was considered mixtures
to
and No(O,),(OH)~ thought
to
L2Pt02
+
in moderate
-7130
RCOCl
6 and substituent
by osmium tetroxide conformation
of
selectivity rin9
of
were
the the
reactant
A conformation
(Table
The stereochemistry process
effects
was the and that
reacted epoxidized
references) oxidation tions)
[350].
for
ethylene
[351]. of
equilibration
factor
of
that
the
determining
substituents
the hydroxypalladation
Studies oxidation
on the
A4-steroic
ring
the
merely
step
A
stereo-
anchored
the
in mechanisms
in acetic
2- and 1-acetoxyethylpalladium(I1)
threo-1,2-
trans-1,2-
of
new homogeneous
was found solution
solutions.
of
of
have been
in aqueous acid
in the Nacker
formation
development
to acetaldehyde
by palladium(I1)
same reaction between
(139)
1) [349]. of
A difference
ethylene
and the
c348].
hydroxylation
was shown to be -trans by the stereospecific from the Nacker reaction
Catalysts
nor-
l
dideuterio-2-chloroethanol dideuterioethane
with
I
0
in the
primary other
of molybdenum was
which 139)
epoxidatic
Mo(Oz)(Cl),(OH)2
chlorides
It was concluded
investigated.
reaction
(eq.
1
‘O-O-C-R
Stereochemical
Acid
yields
acid,
complex
complex
/Cl
l
The epoxidation
In molydenum catalyzed
[347].
peroxyacid
The kinetics by hydrogen
peroxide.
and hydrochloric
agent
to catalyze
[3451.
allylalcohol
The monoperoxide
epoxidizing
LaPto
of
hydrogen
[346].
peroxide
an intermediate
and cyclohexene
to
in nature
were present.
bornene
epoxidation
respect
hydrogen
be the
to give
with
be polar
containing
by &-butylhydroperoxide
catalyzed
order
and were used
and pyridine,
cyclohexene
reviewed
in the
(Nacker In acetic prior
(56
catalytic condiacid,
an
to decomposi-
261
Table
1
Hydroxylation
Olefin
of A"-Steroids
4~~,5a diol,
A4 3a-OAc,
A’
A'
3a-OAc,
19-Nor,
A4
36-OAc,
19-Nor,
AL
Pa-OAc,
A4
2~-OAc,
A’
tion
vinyl
to
2
98
87
13
11
89
77
23
62
38
8
92
was proposed,
while
CO formation-hydride
shift
3,3-dimethyl-1-butene,
gated
cyclooctene,
copper(I1) mechanism using
[3533.
chloride of the
palladium
aromatic
sequences
by palladium
in detail
The
reaction
unclear
complexes,
i-
PdCl,
+
CuCl,
acid
several 140)
the
concerted
oxidation
of cyclo-
cis-2-hexene
solution
%
C3547.
making
Organic
by
was investi-
by palladium
products,
oxidation
(187
conditions
and
of norbornadiene
(eq.
including
The
l-hexene
gives
been reviewed
has
[352].
in acetic
oxidation acid
under blacker
occur
acetate
in acetic
compounds
diol,
>99
acetate
catalyzed
4s,58 76
hexene, oxygen
%
24 A4
38-OAc, 19-Nor,
by 0~0~
chloridethe
synthesis
reactionsofolefins
references)
and
[355].
m
+ OAc
(140)
x
d&L
Y!YzLoAc+ Aco The
oxidation
chlorohydrins
and
of olefins vicinal
examined_
The
containing
chromium-carbon
oxidation
of
reagent
of olefins
with
aryl
nickel(I1)
chloride
pinene
References
by manganese acetate p. 303
and
involved bonds
such
chromate-iodine
en-3-01
dichlorides
mechanism
olefins
by chromyl
as
or alkyl
triacetate
a cis
c356].
a-Iodoketones
141)
produced acetate,
addition
styrene
6-Oxyselenides
(eq.
to produce
epoxides,
process
of organometallic
selenocyanates
in methanol
myrtenol
via
formation
1-hexene,
C357l.
chloride
OAC
produced
by the
and
cyclohexene
were
produced
by the
in the
presence
of copper
C3581.
a-terpineol as well
were
was
intermediates
The
oxidation
acetate,
as other
by a silver
of
reaction
a-pin-3-
materials
or
(+)--CL-
c3591.
262
Oxidation of (+)-3-carene by manganese triacetate gave nine products C3603.
The application
organic
compounds
0
of manganese
triacetate
has been reviewed
as an oxidizing
(61 references)
reagent
_,.SePh
+
I
PhSeCN a
0,
ROH
OR’
100%
and
(141)
PhSeCN CuC12/MeOH +
RCH,=CH
RCH-CH2
,
OMe
-I- RCH-CH2 !iePh
;ePh
I-Octene
was catalytically
a&oxidized
tris(triphenylphosphine)rhodium Tri phenyl phosphine C3621.
chloride
was necessary,
The same rhodium
Triphenylphosphine
porphyrin hexene
catalyzed
oxide
the
complex
There
with
2-octanone oxygen
oxidized
by treatment
at 1 atm and 25O. to
triphenylphosphine
was used to catalyze the oxidation
and phenols inhibited the reaction C3631.
conversion
with
hydroperoxide in essentially quantitative of
and cyclohex-1-en-3-ul,
acetylacetonate.
to
and this
of cyclohexene to P-cyclohexen-l-y1 yield.
&ie
clO%
>87%
oxide
for
c3617.
cyclohexene by oxygen
were 5 x lo3
moles
of
to a 1:l
mixture
and molybdenum product
formed
Iron(III
of
cyclo-
or vanadium per mole of
iron porphyrin C3641. Terminal
alkenes
were oxidized
to
primary
alcohols
by hydroalumination
by lithium aluminum hydride catalyzed by dicyclopentadienyltitanium followed by oxidation of the thus-formed alane.
yields, while terminal olefins gave fair to excellent yields. both
terminal
position
and internal
[365].
Moos-HYPA (eq. nones (eq.
Dihydropyran 142)
by treatment 143)
olefins
[366]. with
reacted
selectively
was oxidatively Vinyl
oxygen
ring
cycl obutanes
at the opened
Dienes having terminal
by treatment
wore oxidized
and palladium(I1)
dichloride
Internal olefins gave poor
to
with
cycl openta-
chlsride/copper(II)
chloride
c3671.
(142)
Primary ch-ioride,
alcohols
oxygen
were oxidized
and an amine.
Benzylic
tnd allyiic
aliphatic
alcohols.
alcohols Secondary
to aldehydes
The best reacted alcohols
by treatment
with
copper(I)
amine was 9,10-phenanthroline.
faster gave
and gave
better
ketones,
but slowly.
yields
than Benzyl
263 amine was oxidized
to benzonitrile
PdCl?/CuClp Oz/HzO PhH, 25O
R
Secondary
oxygen
alcohols
smoothly
provided
were
and
compared
to that
aldehydes
nonaqueous
(eq. and
144)
C3717.
ketones
by
CsF5). C372].
Jones
reagent
air
complex
75% 82%
R =
65X
CH2NHCOMe
salts
unsaturated
for
and
was
While
used
for
kept
in solution
oxidation
of ethanol
the
and a small was
OS;
catalyzed
of
of alcohols
reagent
were
was
reagent
in eq.
oxidized
R = CFs,
C2Fs,
osmium
catalyst
the
145.
to facilitate
piece
all gel
chloride
Collins
alcohols
than
oxidation
2-
a,8-unsaturated
(M = Ru, reactive
was
oxidation
by Collins
secondary
more
the
in methylene
gave
with
be!lzyl alcohol
on alumina/silica
alcohols
chlorochromate
were
citrate
(143)
E-Propanol,
and
proceeded
(PhsP)2M(CO)(02CR)
trisodium
C3687.
by treatment
catalyst.
adsorbed agent
reaction
Primary
catalyst
yield
in high
acetate
chloride
pyridinium
ruthenium
chromium(II1)
of
conditions
R=H
cyclopentanol
oxidizing
The
these
R = CN
usingpyridiniumchlorochromate.
The
The
Chromyl
ketones.
epoxyaldehydes.
aldehydes
to ketones
chloride-sodium
The oxidation
at 25°C370].
of
oxidized
f-3691.
under
R
cyclobutanol.
a neutral,
to aldehydes
tion
4
cyclohexanol,
reacted
gave
'
and a palladium
octanol,
in 90% yield
The
produced
isolation
amalgamated
to
by addi-
mossy zinc
[373].
by a cobalt-o-diaminoazobenzene
[374].
Collins reagent CHO 69%
but
(744)
pyridinium chlorochromate
h H
.* x
CHO
98%
Benzaldehyde chlorobenzene oxidized
was
at 25O
to carbon
of carboxylic Referencesp. 303
acids
oxidized via
to perbenzoic
a radica,l mechanism
dioxide,
and
by treatment
ketones with
were oxygen
acid
by
c3757.
(PhsP)zPdOz Carbon
oxidatively and
cleaved
Rh6(C0)16,
in
monoxide
was
to mixtures
(PhsP)aPt
or
264
Jones reagent
(145)
80%
IrC1(CO)(PPhs)2 peroxide
at elevated
oxidized
temperatures
1,3-dicarbonyl
and pressures
C3761.
compounds in the presence
Hydrogen
of tungsten(V1)
or molybdenum(V1) compcunds [377I]. Chromium trioxide oxidized at the allylic position [3787. alkaloid c3791.
was oxidized Taurocholanic
solution [380-J.
1,4-cyclohexadiene and tri-t-butylcyclopropE The benzylic position of an isoquinoline
by VOFs to give
a 61% yield
acid was autoxidized
to methyl-l&-hydroxy-%-cholan-24-oate Iron(I1)
oxidation
(eq.
induced decomposition 147) C381].
of +-cataline
by ferrous
146)
and methyl lithocholate
of a rigid
The catalytic
(eq.
ions in aqueous
epidioxide
oxidation
led to remote
of paraffins
dMe
such
6Me 61% + cataline
as isobutane
or propane on ternary
C382, 3831.
Naphthalein
salts
to give
products
was selectively copper(I1)
oxidized
reacted
of radical
oxidation
to anthraquinone
bromide in ethylene
Substituted
NiO-A120s-Si02
catalysts
with oxygen in the presence
glycol
(eq.
148j [I384].
was studied of iron(I1) Anthracene
by oxygen in the presence
solution
of
[3857.
e-carbol ines were aromatized by treatment with Rh(PPhs)eCl.
Rh(PPh,j,(CO)Cl or Ir(Ph3P),(CO)C1 (eq. 149) C386, 3871. Isoxazoles were prepared from the dihydro compounds by treatment with Y-manganese dioxide (eq.
150) C3881.
carboxylation
Palladium on carbon effected
via a s-allylpalladium
an aromatization
complex (eq.
151) [389].
with deBoth piperidi
and cyclohexanone were aromatized by palladium chloride or tetrachloroSpi rocycl opentanenaphthalei ns palladate(I1) ion in aqueous base c3903.
265
9”
r
& Me
FeSO,
/* 0
* Me
/‘x Me
COOMe
CHMez ‘. .* 0
+
**
COOMe
28%
(147)
0 0 03
•I-
[email protected]+
Fe(II),
0,
0 (148) a-naphthol +
HO
aromatized
with
contained
rearrangement
in polycyclic
bromide/lithium with
dehydrogenated
t-butanol
.
phosphine
References
stereochemistry
with
with p_ 303
group with
rhodium
potassium
(eq.
153)
palladium
cases were studied
PhsP(CHz)sPPhz
by treatment treatment
junction
carbonyl
(eq.
Cycl ohexanones
with
Aromatization and without
[392-J.
154)
[393].
copper(I1) occurred
a halogenation
Ketosteroids
were acid
The chelating
in
di-
to Ph2PCH2CH2CH=CHCH2CHZPPhZ
or i ridi urn cyclooctadiene C394].
C31113.
chloride-hydrochloric
was dehydeogenated cyanide
152)
by treatment
acetonitrile.
by treatment
Nine
(eq.
in refluxing
of ring
nonconjugated
pal ladium
systems were aromatized
bromide
conservation
of the
over
B-naphthol
complexes
followed
by
H
3 3
i?RhCl
/\-
(149) N R’
R
R = H, Me R’
=
PhCHe, Pr
y-MnO:,
R1 = Ph, n-octyl R’ = H, NO2
(150)
, Me, s-naphth,
COOMe
,,,COOMe
R3 = Me, Ph,
Cobalt(II1) hydrazones, the ly
in fair
coupled
benzylcyanides
methylene
c3987.
cleaving
ketone
C3951.
40% yield
in 35% yield, with
and oximes
N,N-Dialkylanilines by treatment
copper(I)
tosyl-
with
palladium(I1)
C3963.
Benzyl
and 6-phenethylamines chloride
to
were oxidative-
to
and oxygen in
The mechanism of the catalytic oxidation of triphenyl-
to triphenylphosphine
was reported
at
group came from an acetate
to benzonitrile
in about
pyridine C3971.
efficient
2,4-dinitrophenylhydrazones
to high yield
to 4,4’-diaminodiphenylmethanes The extra
amine was oxidized
phosphine
was very
dimethyl hydrazones,
ketone
acetate.
trifiuoride
Aromatic
oxide diazonium
by oxygen and a Pt(Oz)(PPhs)z salts
were converted
catalyst
to the corres-
267
0
OH
CuBr7, LiBr CH$N rfx '
R
R
b
0 85%
-
(153)
o&
_ Ho* 75%
0
ponding phenols in high yield
by treatment
with
CA,0
and
CU(NO~)~
in water.
This procedure was superior in all respects to the acidic water procedure C3991.
Aryl Grignards were oxidized to phenols by treatment with
Referencesp. 303
268
0
t-I&OH PdCl z/HCl ’ 80°, 20 hr
(154)
Hexahydrocolupulone
Moos-Py-HMPA in THF at -78”[4001.
was oxidized
in
cyclohexane and small amounts of alcohols in the presence of copper(I1)
acetate
to give
cyclopentenediones
(eq.
155) [401].
ROH CU(OAC)~ '
(155)
R = CHMez,
RO-
IV.
Reduction There was a great
deal of activity
in the area of catalytic reductions,
with much emphasis on asymmetric reductions and solid phase supported catalysts
The complex from biscyclooctadienerhodium(1) methylphenylcyclohexylphosphine catalyzed in 46-982 yield of pyrrolidine
and 13-67% optical carbamate esters
yield
chloride dimer and chiral the reduction of conjugated acids Chiral diphosphines (eq. 156) 14021.
(I-III) were used as ligands
the reduction of N-benzyloxycarbonylaniline
on rhodium for
in 50-60% optical yield C4031.
Using a long chain ester group on these ligands gave a hexane soluble
catalyst
which reduced the ketone group of c ketoesters
in 99% yield
with
67.3% optical yield [404-J. Structural requirements of the chiral diphosphine ligand in rhodium asymmetric hydrogenation catalysts were carefully studied C405, 4061.
The response
of enantiomeric
excess
in the reduction
of CH,C(NHCOMe)COOH and PhCH=C(NHCOMe)COOH using rhodium(I) complexes of a series of diphosphine ligands was examined. The differences in enantiomeric excess
was claimed
(Table 2).
to be related
to the structural
rigidity
of the ligand
Changing the substrate from the acid to a series of esters, and
alteration of the aromatic group had little effect on enantiomeric excess t4071.
The rhodium complex with the (S,S)bisdiphenylphosphine
prepared
from
269
+
[Rh(COD)C7]2
*
catalyst
(156) R' R'
OH
/
+
+
catalyst
+
Hz
H
R
+
0
0 yield
ee
46%
13.5%
98
67
atropic E-B-methylcinnamic a-methylcinnamic
70
61
a-acetocinnamic
80
44
53
52
itaconic
rx
Ph,P
Ph2
?h2P
N
CH2PPh2
k
;O-t-B"
COCH,
;OO-t-B"
(SS)PPPM
(SS)APPM
(SS)BPPM
III
II
I
H,PPh*
‘cx, N
CH,PPh,
0PPh2 [(diolefin)RhCl]2 d
f ligand
+
=‘OPPh2 IV
Table
2.
Effect
of Chiral
Diphos
on ee
in Reduction
of RCH=C(NAc)COOH
DIOP
R=H
73%
72%
72%
40%
R = Ph
82%
86%
63%
35%
References
p. 303
catalyst
270
(R,R)-P,3-butanediol 92-100% optical catalyst
yield.
C4081.
catalyst
catalyzed
diphosphonite
(Diop gave 24% optical
phenylalanine acids
was observed
the molecular selective complexes
to (R)-Z-phenylbutane
yield
with this
yield
in
with this
yield.)
while
N-acetyl-
Unsaturated
carboxyli
while moderate stereo-
esters
asymmetry induced by olefins
in 60% optical
substrate,
low stereoselectivity,
with unsaturated
C409J.
The importance
of
in the enhancement of enantio-
dehydrogenation of racemic alcohols by (+)neomenthyldiphenylphosph or rhodium or ruthenium was investigated [410]. Asymmetric hydro-
genation
of cx acylaminoacrylic
catalysts
was studied
two carbonyl
groups)
in great
substrates
reduced
in only 1% ee (eq.
reduced
were much less
over
yield
acids
using chiral
biphosphine
“Tridentate”
detail.
gave the best optical
dentate
optical
in 83% optical
acids
IV formed a rhodium hydrogenation
was reduced in only 43% optical
were reduced with quite
selectivity
of N-acetylamino
L-Dopa was prepared
The chiral
that reduced a ethylstyrene
yield.
were
the reduction
V based rhodiu
substrates
yields
(olefin
(89-96% ee) whi!e
and
bi-
a Methylcinnamic acid a-Aminoacrylic acids and esters
stereoselective.
157) [411].
(S)-RhC1[PhaPN(CHPhMe)CH2CH2N(CHPhMe)PPh2]in49-843
II41 22.
+ gCODRhC1]2
NaBF,
+
catalyst
(157) CN
,COOH , CH,=C ‘NHCOCH$l NHCOPh
I ’ ,(h
Pd;;;;R
Me
A -
r(
NHCOMe
Ph
The use of chiral
ferrocenylphosphine
effective
for
hydrosilation C413,
4147.
(4-7%)
optical
chiral
bidentate
was derived carboxylic
asymmetric
reduction
of ketones
and for
Atropic yields
using
phosphines
the
C4157.
ligands
.
asymnetric usual
acid,
Grignard acids
rhodium
type
r( Ph
on transition
of a-acetamidoacrylic
of the
Prochiral
COOH
, 9% ee
and a-acetamidoacrylic
from (+)-camphoric acid
NHCOMe
-
, 51% ee
Ph
reduced in 89-96’i ee
) 1%
metals acids,
cross
was
for
coupling
cationic
catalysts
(-)-nopinylamine esters
asymmetri reactions
in low
were hydrogenated
Ph2PN(R)-CH2CH2N(R)PPh2
unsaturated
-
containing where
R
and (-)-pinane-3were
reduced
in up
271 to 76% 158) the
optical
E4167,
yield
while
corresponding
using
catalysts
bisphosphine
VIII
acids
ee
OPPh2
in 54%
f
derived based
(eq.
from
bisphosphite
catalysts
159)
C4171.
[(olefin)2RhC1]2
+
VI
were
used
The
complex
(eq.
to reduced L,Rh(amine)Cl
catalyst
0PPh2
(158) COOMe
ii
)_( -
+
100%
catalyst
H2
conversion
76%
optical
yield
NHAc
Ph
VII Ph
NHCOMe
H f
)_( H
H2
-
RhL"
(S)-PhCH&COOH iHCOMe
COOH
54” m ee ./here the
amine
amidocinnamic were
acid
obtained
phosphinite catalyst
was
in 80% yield
in the derived
was
corresponding
the
Rus
[421].
References
Ru4
p. 303
The
optical
system,
were
as
Reduction
used
acid. while
silica yields but
of the
catalyst,
ee [418].
reduction
High
catalyst
Up to 58% 61%
the
type
gel were
rate
with
and
was
ten
precursors
asymmetric
of a-acetamidoacrylic
used
comparable
induction
induction esters
was
using
(77:A)
insoluble
A Rh-OIOP
to reduce to those
times
for
yields
an
C4191.
H,Ruk(CO)sC(-)DIOPJ,
syrnnetric
of a-acetam-
optical
of P-phenyl-1-butene
compounds
(Z)-a-methylcinnamic with
20%
the
6-o-triphenylmethylcellulose
homogeneous
Ru~(CO)~~[(-)DIOP]~
catalyzed
to macroporous
acid.
cluster
and
hydrogenation from
attached
acetamidoacrylic
Ruthenium
d a-phenethylamine
slower
CLof the [420].
and the
reduction
was
of
observed,
obtained ruthenium
with catalysts
272 of the very
type
low
(~22)
resembling c4233.
RuClzLz
where
optical
DIOP
Benzil
yields
(VIII was
L was
and
iXj
reduced
the
chiral
sulfoxide
of reduced
product
led
ee
to 25%
to benzoin
EtCHMeCH2SOMe
in 79X
Using
C4221.
in the
reduction
ee using
containing
a ligand
genation
catalyst
C4251.
The reduction
The
of
change
The was
by rhodium hydride
ethylene and
black
benzene
over
to the
polystyrene
tri chl oride.
and
a cobalt
group
chirality
recognizing
(PhsP)sRhCl
supported
was
for
of this
glass
was
This
beads
The
system
transition
treated
polymer
polymer
[428].
counterpart
the
reduction
C4291.
chloromethylated,
reactivity hexene
of
with
which
changed in the
studied
catalyzed
the
support
Aging
under
benzene
hydrogen
led
ports
chloride polymer
measuring maximum
this (eq.
to the
[430].
reduction
dienes of Ti,
of synthesizing polymer 160)
attached
curve
extent
catalysts
rates was
Hf,
relative
observed
Nb,
such
to
porosity
were
The
reduction
loading
Ta,
for MO
and
for
W into
interactions
hydr of
polymer
sup-
and
and
hydrog
among
was probed by
loading.
Rhodium(I)
the
anion,
dichloride,
as Cp2TiC12
polymer
for
polymeric
introduction
cyclopentadiene metal
cycle
active
with
active the
of
and porosity.
particles
complex
of metal-metal
[433].
the
of
A method
polymer-bound
-The
C4321.
Zr,
homogeneous
was reacted
rhodium(I1)
bis-cyclopentadienyl
metallocene
hydrogenation in this
with
for
of metallic
[431].
of cyclocatalyst,
[(olefin)2RhCl&.
Rhodium trichloride
and
complexes
with
catalysts
formation
its
in their
to be a function
a paramagnetic
of monoolefins
consisted
treating
treated
boro-
effective
as was
differing
supported
and was found
hydrogenation
cyclopentadienyl
and
different
PhzPCHzPPhz producing genation
resins
[427
followed
sodium
metallocarborane
olefins,
at 68".
acid,
with
of
in the
abruptly
polymer
treated
supported
of hindered
phosphinated
was examined
bet
have
on a copolymer
was
o-aminobenzoic
was then
first
Polystyrene
these
hydro-
determined
function
~3,3-(Ph~P)~-3-H-4-(polystyrylmethylj-3,1,2-RhC~B~H~~l,wasan catalyst
catal.
monooxime
asymmetric
diphenyl-p-styrylphosphine
activity
ascribed
to give
hexene
of 2,3-butandione
of
a bis-dimethylglyoximato
catalytic
Chloromethylated
cobalt
ac
[426].
divinylbenzene
gas phase.
condensation
The structure
containing
(93 references)
styrene,
by the
[424].
complex catalysts with
Metal
reviewed
itaconic
IX
formed
1,3-propanediame
sulfoxides
of
a chiral
VIII
with
gave
The
catalysts
expected imnobilized
373 on phosphinate
styrene/2-20%
divinylbenzene
f 2
copolymers
were efficient
for
-i-
0
0
_3HCl
CpzMClz
(160)
G
/Cl
8
&Cl 0
the
hydrogenation
concentration
of olefins,
diolefins
and the role
and alkynes.
of uncoordinated
The effect
of substrate
phosphine was examined [434].
Transition metal complexes supported on phosphine modified silica gel carriers were two to four times more active as hydrogenation catalysts than the corresponding homogeneous systems. LaRhHzCl
,
LsRhCl
LzCoC12,
3,
tetrachloropalladate in the presence the reduction -4361.
L$liC12,
of ally1
alcohol
hydrogenation supported ethylene
than were their
on the polyion
and cyclic
dienes
system consisting phase,
in an immiscible
the solubility were obtained Treatment of
sodium
al kenes
of the olefin with this of
hydride
and
al kynes
catalyst
in
and propane the hydro-
olefin
phosphine
ladder
with rhodium(I)
[438]. for
for
tol!ards Colloidal
acid
olefin palladium
and poly-
the reduction
of linear
An unusual
was to use a two-phase
and product
Ph,P(o-SC3Na-Ph)
alkane as the organic complex of rhodium
aqueous phase.
The reactions were governed by in the aqueous phase. Very high conversions
system c4401.
10 equivalents
of
iron(II1)
THF and A-butanol (including
Ketones reduced only slowly, References p. 303
selective
homogeneous catalysts
and the water soluble
trichloride
and treated
were much more active
homogeneous analogs
of the substrate
a catalyst
were used for
to monoenes at 30” under hydrogen [4391.
approach to heterogenizing
LsRhHClz, Potassium
to produce
complex composed of polyacrylic
imine was the highly
,
coated with an organosilicon
phosphinated catalysts
L2NiBr2[4357.
propionaldehyde
on zeolites
Silica
LsRhCl
were
BaS04 or alumina and reaJced
hydroxides
to n-propanol,
C4371.
These supported
.
L2PdCl 2 and
supported
polymer was chloromethylated,
studied
on carbon,
of tetraalkylammonium
of cyclopropane
complexes
complexes
was supported
Platinum catalysts
genation
The
produced
phenylacetylene)
and olefins
could
chloride a black to
with
60
powder
al kanes
be reduced
equivalents which
reduced
quantitatively.
in the presence
274
of ketones. olefin
Vinyl cycJohexene
in 98% yield
hydride
in the
a black
catalyst
dienes
Treatment
[r4411.
same proportions which
also
A similar
by titanium hydride
or zirconium
Reduction
hydride
by dicycJopentadienyJpaJJadium
of the
reducing
reduction
cf
cataJyst the
reduction
hydrogenation
shorter
Rh(PPhs)sCJ duction
were compared with
Each reduced
3,7-dimethyloctanol. Palladium specific conditions
With
while
with
2tn carbon reduction (eq.
the
the
161)
[450].
K region
aluminum
olefin
[4441.
catalyzed
stereospecificity and BzHs in the
whi7e
on carbon
the rhodium
C4467.
were very
active
The catalysts
irreversibly
deactivated
J-Octene
was hydrogenated
by
to citrone77ol
one it
catalyst
The hydrogenation
the
first,
rethen
to
was considered
high yield
aromatics
and
in their
was simultaneous
for
of polynuclear
this
and
where L
Ru(PPhs)sClz
and rhodium metal
geraniol
over
PhP(CHzCHzPPhz)z
was the HaCoL species
homogeneous catalysts
was an efficient of the
studied,
The complexes
heterogeneous
was catalyzed
hydride
Palladium
triphosphines
catalyst
ruthenium
of the
on substituents
c447].
c4481.
in
dienes,
hindered
RhHzCJ(PPhs)z
olefins
of cheiating
phosphine
hydride
aluminum
was made.
but were
The most active chain
catalyzed
gave CHs(CH2)4CH(OH)CH=CH2
depending
dimers
least
A comparison
six
and
was
lithium
and CIr(COD)Lpy]+PFs
bridged
of geraniol.
sequentia7,
trans,
complexes
PhPt(CHa)aPPhz&.
all
alkanes,
resulting
nonconjugated
with
sodium produced
dichloride
With
on carbon,
of olefins,
of hydrido
and rhodium
was the
with
to
aluminum
added tc the
14457.
palladium
CIr(COD)L21+PFs-
formation
titanium
the exocycl i c
with
by HA7(NRz)z,
homologous to a-pinene
gave from 40-95%
compiexes
cobalt
systems
alkynes
lithium
dichloride
reduction
olefins
gave >90% trans
for
with
tetrachloride.
aluminum
selective
and
of reactivity
of CH,=CH(CH2)sCH(OH)CH=CHz
in a highly
of t-amylalcohol
and alkynes
hydroalumination
and lithium
acetate
presence
alkenes
The order
at
of nickel(I1)
Dicyclopentadiene
of alkenes
upon hydrolysis.
c443l.
excl usi ve reduction
in the
reduced
to monoenes C4427.
the hydroalumination reduction
underwent
[449]. regio-
under mild
of a-methylstyrene
by HMn(CO),
275
97% proceeded metal
by a free
hydride
pressure
to
using
radical
the
the
cluster
Coq(CO) 11 was inactive. of
reactions
for
path
substrate
involving
[4517.
catalysts Addition
the active
hydrogenated
to e-Z-butene
over
nickel
hexahydrate
sodium
chloride
borohydride
unsaturated cycl ohexene
The catalysts
.
selectively
reduced
efficient
were very
to monoenes
sensitive
cyclooctadiene was reduced to cyclooctene cycl ododecatriene decadienoate c4551.
to trans-cycl
to ethyl
ododecene
complex
and long-lived
duced
to cyclohexanes (eq.
162)
Conjugated [459], [460,
under mild
was highly
4611,
chloride
and with
reduction this
conditions
of
catalyst [457].
using
and all
2-acetyl -4,9seiectively as a catalyst was an efficient arenes.
Extensive
system Arenes
isomers
from both
were re-
[MesCpRhCl],
cis
fashion
100% selectivity
IrCl(CO)_(PPha),
reactions
were reduced
the
acid
IrCl(CO)L,
at 80-120”
(L = various
homogeneous
was prepared
hydrobromic
using
solvent
IrC1(CO)L2
for
conditions
with
the
with
were
In this
as a catalyst.
were the major
[458].
esters
catalyst
under mild
for
stereoselective
IrC1(CO)(PPhs)2without
efficient
with
of
to
trans-1,5,9-
n6-CsMesRu-n4-CsMes
was noted
and H2 + perdeuteroarene
The reaction products
catalyst
exchange
&,trans -3 and ethyl
with
reduction
Polyenes
to cyclohexenes
using
ruthenium,
homogeneous
hydrogen-deuterium 02 + arene
of
reaction
the
catalysts_
(93%)
was reduced
homogeneous
[456l.Aa-arene
(87X)
2-acetyl-4-decenoate
Neat 1,3-cyclohexadiene
in a photoinduced
(891),
[453].
exclusively
[454].
RuCl,(PPhs),
rates
hexahydrate
for
was reduced
air
over
chloride
catalysts
1,3-Cyclohexadiene
the
was selectively
complexes
or cobalt
low
while
enhances
1,3-Butadiene
cobalt(I)-bipyridyl
in OMF produced
compounds.
phosphites
[452]_
from the under
and CosRh(CO),,,
trimethyl
catalyst
atom transfer
was hydrogenated
Co,Rh,(CO)l, of
Treatment
of
hydrogen
Styrene
phosphines)
reduction
by treatment
and water
and photoactivation
and 10 atm of of of
hydrogen
[462].
A very
unsaturated H,PtCls
in alcohol
esters
and stannous
solvent
The
[463].
cationic rhodium complex CRh2(diphos)212f was an efficient homogeneous catalyst acids, transfer catalyst.
for etc.
the
reduction
[464].
hydrogenation The olefin
Molybdenum hexacarbonyl
References p. 303
of
Conjugated process reduced
simple ketones using
alkenes,
acrylic
were reduced
and amidoacrylic by P-propanol
via
a
RhCl (PPhs) s and RuCl2( PPhs) s as
first,
followed
in refluxing
aqueous
by the diglyme
carbonyl
C4651.
reduced
a variety
of
H2
+
15-%&l 15 eq. Et,N/catalyst Z-propanol
arene
+
'
hydrocarbon
(162) PhCOCH,
e.g.,
-f
PhNMe,
but,
Low
-+
PhEt
cobalt
(97%)
and
triisopropylphosphite n3-ally1
catalysts
for
saturated
ketones
composition
copper(I)
carbonyl bromide
with
acyclic
Sulfonated
soluble
reduction
of
catalyst
ketones
decanal
were
and
made
esters.
Both
HaCoLa.
ketones hydrides
and of
reduction
by treatment
complex")
"Li complex"
(14661.
selective
conjugate
"Na complex"
nitriles
and
was
used
of the
and
type
of
of
or
was
gave
best
for
highest
complexes
carbonyl
esters as
hRu(AcO)Ls
were
ligands
the
yields
reduced
and
groups
were
dependent
inert
ynones
(eq.
to make
RuClzLz
in aqueous solution.
oxoacids
IrH3(PPhs)s
which
were
with
reduced
hydrogen.
reduced
not
acetic
aldehydes
Conjugated reduced
to the
10 atmospheres
of hydrogen
compounds
not
were
type
were
Copper
were
yield
upon
the
water
for
The
163)
the
rates
of
pH of the
c4697. of
of
and
of the
the
("Li
The
triphenylphosphine
olefin
system
atmospheres
for
complexes
the
while
cataiysts
solution
Treatment
while
ketones
of unsaturated
reaction
(75%),
< 5% reduction
in high
hydrogen,
[467].
LiAlH(OCHs)s
, while
PhNO,
of a,&unsaturated
efficient
The
PhX,
ketones
amides
complex").
reduction,
i468?.
aqueous
COOMe
Aidehydes, ketones and halides were reduced at rates com-
parable to enone
reduction
("Na
unsaturated
in poor yield.
reduction
very
either
cycl ohexenones
of
PhOH.
L3 with
and
compounds.
NaA1H(OCHzCHzOCH,-)2 reduction
the
were
with
-+
complexes
cobalt
hydrogenation
conllrgated
PhC:CH,
a,&unsaturated
amides
unspecified
PhCOOMe
(73%)
including
by treating
to the
(lOO%),
u
NMe,
olefins,
valent
prepared
&ZHa
+
PhCH=CH,
conjugated
u
0
reduced
at all
alcohols and
, and
50-80° benzyl
acid
produced
to alcohols
aldehydes c4707. using
at 80-llO",
underwent
10
complete
reduction
Benzaldehydes,octanal
RuClz(PPhs)s
in benzene_ alcohol
a homogeneous
was
as a catalyst
Ketones not
and
aryl
hydrogenalized
and at nitro
277
2LiAlH(OMe),
+
CuBr
NaA1H2(0CH2CH,0CH,),
'" k THF
+
CuBr
"Li
complex"
"Na complex”
+
RI = R2 = H
Li complex
R'=H RI
/-L
84%
3 R2=Me989
R1 = R2 = Me
Rl
2 92%
0
(163)
0
R
RCH,CH&R
R
R'
R*
CO_$le -
Rlti
c4717.
Cat-ionic
to reduce
1 atmosphere, (prepared
in methanol
in very
high yield
hols,
which
although
corresponding saturated niclrel(I1)
alkynes
in some
cases,
to alkenes
methyl
presence
diphosphine p. 303
oxide,
acetoacetate
C4771.
and
as
catalysts
in methanol
at
aldehyde
only
the way
the
was
of ketones
with
at 40-65O,
lo-20
systems
reduced
modified
by the
addition
produced
a
to saturated
double
Similar
to alcohols
Acetone,
borohydride
saturated
boro-
were reduced
adamantanone
sodium
sodium
ketones
(NaOH).
all
in THF
with
reduced
base
aldehydes
Treatment
yield.
in toluene) which
reduced
used base
of Rh2H2C12(COO)(PPh3),PhCH,
strong
with
were
of strong
alco-
isolable_ bond
sodium
hydride/
hr reduced
olefins
The
to produce
ketones
to alkanes
and
[476].
nickel
of aluminum
effective
the
catalyst
E4757.
in high
Reduced
References
conjugated
acetate/g-amyloxide
to alcohols
halides
reduced
aldehydes
of
benzophenone
palladium
82%
presence
a catalyst
of nickel
97%
R1 = H3 R2 = Ph
hydrogen
presence
84"' ,'D
R1 = R2 = I&
Treatment
and
produced
in the
Reduction
catalyst
4737.
acetophenone,
2-hexanone,
duced
C472,
68%
of rhodium(I)
in the
CODRh(Cl)PPh3
hydride
C4741.
complexes
to alcohols
25°C
from
0
bipyridine
ketones
98%
R1 = H, R* = Me
OBe
-+
t/ RI
R = t-Bu R = ;h
to CH$ZH(OH)CH$OOMe
reduced
Rhodium(I)
catalyzed
the
the
optical
complexes
reduction
of
of tartaric
in 85%
yield.
containing a-ketoesters
Thus
optical Raney
the chiral to
chiral
acid yield.
nickel
reThe
was
less
pyrro:idine lactates
in
278 THF at 25O and 20 atmospheres [478].
Hydrogenation
rhodium
catalysts
3,17over
ketones
simpler
gave
cycl ohexanones,
less
bulky
quinones
to
[482%
alcohol
reduction
high,
with
olefin
reduction
ductively
of
it
lithium
LzNiCls,
FeCls,
source
hydrogenation
Mo(N2)(diphos)2
tertiary
by
isopropanol.
epimers
using
amine
carbony
rhodium
under
0x0
reduction
substantial
remained
or
complexes
alcohols
for
reduce
HsP(O)OH
rhodium(I)
aldehydes,
was
amounts
active
of
when attached
PhCH=CH-COzCHzCH-CHPhwas re-
of
the
palladium
or platinum
benzyl,
aryl
halides transfer
and
metal
have been by the
halides
CuI and ZnBr with
LiAlHJNiClz
material
TiCls,
VCls,
lithium
and LiAlHtJCoClz
aluminum
systems
re-
and aryl
bromides
in good yield
of
copper
hydrides
(LiCuHz,
LizCuH3,
prepared
by the
reaction
of
were found and
to reduce
tosylates
14881.
acetate
ZnCle,
MoCl s,
or zinc
ally1
halides
were reduced
to the
hydrogenation
lithium
primary
in moderate
WCls,
Mo(OAc)z
reduced
to hydrocarbons
hydrocarbon
from secondary
and nitrobenzenes
yield,
and
as well
cyclic
Cp2TiC12).
reduced
and secondar
C4891.
palladium
amines to
and
by
(Ni(OAc)2.
primary
by using
were
halide
cuprates
iodides
was reduced
and metal
chloride
alkyl
alkyl
to good
l-Bromonaphthalein
sodium t-amyloxide
ZrC14,
Halobenzenes
effected
transition
NiC12,
halides
cyclic
hydride,
CrCls,
organic
of reductions
the
CoC13,
chlorides
from nickel
[490].
study
low yield
sodium
reducing
tertiary,
LisCuHs)
yield,
of
catalyzed
for
work a series
in very
The reagent
that
secondary,
mixtures
alkyl,
to
to the more stable
excess
Finally,
aluminum hydride,
in excellent
fluorides
and
PhCH=CH-CHzCH=CHPhover
FeCls,
was found
In related
Aromatic
to
in THF/aq.
to ally1
The catalyst
[485x.
reduction
FeC12,
Li ~CUHL,. Li JuHs, with
and
was used
to cyclohexanols
specificity
unsaturated
new systems
the
primary,
[487%
source
by isomerization
In an extensive from
MnClz,
hydride,
With than
[4861.
developed.
duced
[480]. faster
by transfer
Aminophosphine
were reduced
was observed. polymer
A variety
resulting
on carbon
hydrogen
Rh2C12(CO)b
decarboxylated
in methanol
CrCls,
from
aliphatic
to an insoluble
5a-cholestan-3-one
reduced
to cyclohexanol
With cinnamaldehydes,
while
while
from cyclohexene
of cyclohexanones
aldehydes
prepared
conditions.
3-axial
same results
systems
palladium
t4831.
was accompanied
Conjugated
catalysts
the
gave
with Steroidal
of 5a-cholestan-3-one
36-01,
as the
catalyzed
t4847.
at C-3 to give
catalysts
over
as catalysts
The reduction
reduced
excess
yield.
in high
the equatorial
was reduced
MoHk(diphos)z the
alcohols
hydrogenation
hydrogenation
hydroquinones
a-phenethyl
enantiomeric
in isopropanol/HCl
c4811.
transfer
Cyclohexanone
using
axial
bul ky 4-substituted
substrates
Catalytic
gave
Platinum
in 36-764
cyclohexanones
In contrast,
catalyst
38-01.
axial
hydrogen
were selectively
C4791.
palladium
gave
of
unhindered
selectively
and 3,20-diones
hydroxy
the
of
chloride
as the benzenes
hydrogen and
amines respectively, by triethylarrmonium formate using palladium on carbon Nitrile and nitro groups reduced more slowly, olefin and as the catalyst. Ester, chloro groups were comparable, while bromides were the fastest. amide and ether
groups were tolerated
Nickel
reduced tri-
carbonyl
while
aldehydes
were reduced [491].
and dihalides to monohalides under mild Phase transfer conditions were used for the
conditions (eq. 164) C492Ij. dicobalt octacarbonyl reduction studies
were all
c4931.
Halogen was reductively
of a-bromoketones
aryl methyl ketones
except
eliminated
to ketones.
The ketones
for 1-adamantylmethyl
from haloalkanes
ArzCH-CXs w
ketone
by chromium(II),
ArCHCHZX THF
40-60%
(164)
copper(I) chloride
and tin(I1) with
C4941.
lithium
in 96% yield,
cyclododecanone
opened to the allene treatment
while
14951.
in high yield.
The acid
e-nitrobenzoyl
chloride
enones and dienones by treatment
were reduced
underwent clean (eq.
of chiral
to 80% ee (eq.
studied
and acetyl
with triethylsilane
aqueous isolation
166) C4981.
were benzoyl, furanoyl, hexanoyl, Cinnamoyl chloride and
1,4-reduction
[496].
to give
tetrachloride
Hydrosilation
Cyclohexenone
to
were ring
chloride.
and titanium
165) C4971.
rbromium(I1)
were reduced to aldehydes by anion in methylene chloride at 25”
in O-20% yield
rhodium(DIOP) complexes
hydrosilation followed anone, trihydrosilanes References p. 303
chlorides
of
a-bromocyclododecanone
1,1-dibromocyclopropanes
Acid chlorides ferrate
, e-bromobenzoyl
from treatment
reduced
with hydridotetracarbonyl
cyclohexanoyl
presence
The reagent
aluminum hydride
Conjugated
saturated
of a ketoesters
produced lactate
ketones
followed esters
by
in the in up
was reduced by LaRhCl catalyzed
by aqueous workup. Monohydrosilanes gave cyclohexgave 2-cyclohexen-1-01. while dihydrosilanes gave
280
enol ether
in 99% yield
octacarbonyl
cata7yst
plexes
by treatment
hydrazones
(85 references)
hydrazines
over palladium
reduced by cyclic
with phenyldimethylsilane and dicoba7t Hydrosilation catalyzed by group VIII com-
CSOOl.
has been reviewed Substituted
Cyclohexenone was converted to its silyl-
C4991.
mixtures of both products
C5017.
were synthesized on carbon C5027.
amines,
particulariy
by the hydrogenation of phenylAromatic nitro compounds were
indolines,
using rhodium trich7oride
0
+
00 I,
I!
R’-C-C-OR2
+
TiCl,
RsSiH
l
CRh7* + Ht
R3R4SiH2
H?O
&,CO,,R
PhH
I OH
R1 = Me, Ph
80-90% yields
R2 = n-F?-, nBu, i-Bu,
Et
30-80% ee
also 0
+“’
CH3 \
-
9
0
0 95-100% up to 84% optical or ruthenium trichloride halides
were less
as the transfer
reactive.
hydrogenation
Nitrosobenzene
was detected
yield
catalyst.
Pa7ladiur
as the inter-media:
Phase transfer conditions (benzene/aq. sodium hydroxide, benzyltriethylamnonium chloride) were used to reduce aromatic nitro compounds to
c5031.
the corresponding c5041.
anilines
The same chemistry
in 85-901 yields
by Fe(CO)s or Fes(C0)12
using 2-32 Cl87 crown-6 as the phase transfer
281 catalyst
was
reduced
also
nitroaromatics
compounds
reduced
converted
nitro
chain the
carried
out
to anilines
to the groups
deoxysugars
in 58-97%
aldehyde
in 32-77%
167).
The
of nitromethane
nitro
Chloronitrobenzenes
were
reduced
and
palladium
yield.
sugars
nitro
Titanium
of C-formyl
were
readily
protected
trichloride branched
available
glycosidulose
corresponding
on carbon
in methanol
Aliphatic C5067.
synthesis
the
to the
chloride
yield
in the
with
amines
by hydrazine
Chromium(I1)
to aldehydes
(eq.
condensation
[505].
from
[5077.
chloroarylhydroxyl-
[508].
(167)
Molybdenum acid
hexacarbonyl
solutions
to the
reduced
corresponding
tetrafluoroborates
decomposed
presence
catalysts
when
of copper
either
reductively source)
or Cl81
cleaved
and
Alkyl, with
copper
molybdenum
was
halides,
nitriles
and
nitro
by treatment
with
octacarbonyl
coupled
carbonyl
The
were
obtained
with
simple
were
unreactive
Pd were
verted
hydrogen As
compounds
c513-J.
C51.51.
of the
monoxide
was
p. 303
and
of
Co,
reduced
in the
was
Azoarenes
noted were
(hydrogen
at
were
was
[512].
reduced
olefins
reduced
to alkanes
Iron
presence
lost.
worst
The
(40%)
and
penta-
best
yields
obtained
sulfonyl
groups
of
in the
dicobalt
of tetra-
was
to mixtures
by hydrogenation
B-
presence
[516]. with
potassium monoxide
Mn
Ru,
Fe,
of
also
linear
OS,
Mn,
Cr,
a catalyst
to hydrocarbons to metal
compl'exes
to a mixture
Co,
to generate
(mostly
increased, increased alcohols
Ni,
which
Cu, con-
methane
the
same
esters,
whi?e
C5147.
in the
was
the
The reagent
ketones,
hydroxide,
olefins 145"
by treatment
This
epoxides,
epoxide while
yield
yields.
potassium
esters,
oxide
to sulfides
7595%
oxides,
the
of potassium
Fe and
in
in 88-100%
(95%)
Styrene
carbon
acid
to olefins
of graphite
ratio
reduced
and
Ketones,
with
[510].
were
to tetrasubstituted
complexes
Arenediazonium
fluoroarenes
No decomposition
present
Thioketones
pentacarbonyl
phenylacetaldehyde
treated
the
activity
References
acetic
phosphine
epoxides
and
C5111.
sulfones,
compounds
Pt and
cobalt).
in
alkyiepoxides.
and
not
sulfoxides
stereochemistry
rhodium
Laminar
on asbestos
them
C5091.
of arenes
crown-6.
was
by KaW2Cla
iron
in carboxylic
upon reaction with cyclohexene
withaketoepoxides
phenylethanol of cationic
Cl81
effected
deoxygenated
methylurea.
and
benzyl
compounds
N-carboxylanilines
crown-6
hexacarbonyl
transformation tolerated
and
nitro
to mixtures
to anilines
5% palladium aryl
aromatic
with
catalytic
15171. (methanol,
Carbon ethanol,
282
propanol and butanol) when treated Using
room temperature &187. solvent
at 180°
a 3:1
of
hydrogen
with
a catalyst
The use of
iron
pentacarbonyl
and alkali
and water
the water
monoxide A catalyst
[520]. sodium
iodide
gas shift
8.4
mnol of
hydrogen
7.6
mm01 of
carbon
168).
monoxide
amounts
2-methyl
of
and carbon
time
of
about
gas shift
[Rh(CO)zCl]z
giving
was consumed
phase
with
carbon
After
monoxi
45 hr,
were produced,
while
platinum
in acetic
acid
and exo-2-methylnorbornane
reactions
[522].
a day.
over
7-methylnorbornane
vapor
acid
C5211.
3-methylnortricyclene
compounds
with
was investigate< acetic
at 400 nm~of
dioxide
C519-J.
olefins
reaction
cycles
carbon
was converter
minutes
in glacial acid
nine
mnol of
monoxide
lo-15
to hydroformylate
hydrochloric
catalyst
of
In contrast
most
of
and 8.6
Hydrogenolysis equal
via
and concentrated
was a water
gave
turnover
consisting
as a catalyst in molten NaCl-2AlC
Ir4(CO)1z
mixture
to alkanes carbon
(Me2CHCH2)2AlH and CPnZrClz at
with
over
Similar
supported
reactions
of
metal
the
(eq.
catalysts
cm\
propellanes
tricyclo[4.4.1.01~6~undecaneandtricyclo[4.3.l.01~6]decane
were studied
[523-j.
Lb
Me
Benzyl
ethers
from indoline
were hydrogenalized
using
rhodium(II1)
palladium(I1)
chloride.
hydrogenalized
these
by treatment
catal>
amount of
‘ic
[5261,
Functional A.
[525].
metal
catalysts
by alloys
addition
of
iodine,
halides
cyanogen cuprate
halides
of
has been reviewed
and few side
halides
ring
prepared cuprates with
and cyanogen [528].
presence
of
a
carbon-carbon
(18
references)
clusters
0271.
products
in 74-90X
regio-
to terminal
iodide.
Aryl
alkynes,
were convert
N-chlorosuccinimi,
The stereochemistry
amines
were converted
and copper(I1)
were obtained
and stereospecif
in this
to
halide.
reaction
of
the
aryl High
with
fifteen
The following functional groups were tolerated
by this
Under similar
by the
N-bromosuccinimide,
with t-butylnitrite
substrates.
in the aromatic
alkyl
by treatment
bromide
by treatment
Me c5297.
cuprates,
was retained
representative
aryl
were hydro-
in the
The hydrogenalysis and bimetallic
were also
alcohols
chloride
and
Group Preparations
bromomagnesium
ed to vinyl
yields
Ally1
hydrogenation
acetate
Hal ides
Bromomagnesium vinyl
vinyl
propylmagnesium
L2NiCl2
supported
r-5241.
(168)
by transfer
palladium(I1)
and B-phenethylacetate
conditions
with
as has catalysis
V.
to toluene
chloride,
Benzylamines
under
genalized bonds over
$ +&
H;;c +
reaction:
conditions yield.
NOz, MeO, COOH, Cl, aryl
A range
of
hydrazines substitution
F, CFs, H and
were also patterns
converted was
to
tolerated ethyl
deamination
out in the presence acrylate
(eq.
When this
C5307.
carried
and styrene,
169) 15317.
than they
aryl
The yields
halide
RON0 CuC,, + MeCN
AX
by A-butylnitrite
was
such as acrylonitrile,
added to the conjugated
were considerably
the Meerwein reaction
were using
ArNHz +
of arylamines
of Michael acceptors
better
using
olefin
this
procedure
(ArN2).
ArCHzCHX ;1
(1691
X = CN, COOEt. Ph Ar = e-NOzPh (93%), g-N02Ph (74%), e-MeOPh (83%), E-ClPh (81%), p-MePh (73%),
2,4,6-ClsPh
Alkynes were converted than 80% yield
to mixtures
by treatment
in acetonitrile
(92%),
(eq.
with
2,4,6-(MeO)sPh
(0%)
of E and Z vinyl
copper(I1)
170) [532].
dihalides
chloride
in greater
and lithium
Chromous chloride
(170)
E 95%
95:5 E:Z
Z R = Ph, R’ = Et
R = Ph, R’ = Me 94%
98:2 E:Z
R = Ph, R’ = t-Bu
R = Ph, R’ = H of N-haloamides yield,
also
1-Octyne
urethanes
chloride
promoted the addition
CuCl ?-Li Cl MeCN
RCXR’
in fair
Ph (71%),
to olefins.
N-Chlorocarbonates
but cyclopentene
reacted
gave
in low yield
to conjugated
dienes
only
(eq.
was also
94%
95:5
95%
21:79 E:Z
added to steroidal
20% yield
171).
of
addition
The addition
studied.
Both 1,2-
E:Z
olefins
product.
of N-chloroand 1,4-addition
occurred [533]. The reaction mechanism was studied and was shown to go via a radical chain pathway [534]. The complex (CO)kFeNMe3, prepared from trimethylamine tetrachloride
and iron pentacarbonyl,
to olefins.
ment as well chloride
oxide
Bridged polycyclic
as addition
in a 2:l
(eq.
mixture
predominantly
cis
60-708 yields
C5361.
open epoxides
to trans
Ferric than
completely
general.
Stilbene
References
p. 303
C5377.
the addition
with chromyl
oxide was rearranged
to produce
of regioisomers
in ether was an efficient in high yield.
of carbon
underwent rearrange-
reacted
and acetylchloride
as mixtures
HCl or magnesium bromide.
or better
reagent
chloride
chlorohydrins
be as good
by this
acetates
olefins Olefins
172) [535].
of dichloromethane
chlorohydrin
catalyzed
in
reagent
It was claimed
to
However, it was not to diphenylaceta?dehyde
to
284
RO-C-NHCI Fi
+
NHCOOR 79%
f
cc1
(CO),FeNMe,
ClsC
I+
1
90% I
and
j/j&
(172)
-OF ClsCCH, 80%
B.
Amides, Nitriles
Terminal
acetylenes
underwent
a regio- and stereospecific cis
addition of alkylcopper halide/magnesium
halide complexes to produce ter-
minal vinyl cuprates which were converted to substituted acrylonitriles by treatment with ClCN, PhS02CN C538J.
or TsCN in greater than 90% yield (eq. 173)
Cyclic ketones were c!eaved to w-cyanoesters by treatment with
NasFe(NO)CNS
(es. 174) L-5391. An angular nitrile group was introduced
into decalin systems by conversion to iron cyclohexadienyl cationic complexes and treatment with sodium cyanide (eq. 175) C5407.
The addition
of hydrogen cyanide to olefins has been reviewed c5417.
LWI R
R-CaCH
+
[R'CuXxgHal
-+
H
MgHal
-
I
cux
-
YCN
H
R
(173) R'
N >90%
/-COOR NaqFe(NO)(CN)< f
[complex]
Hi, ROH 'YLCN
I n = 3, 4, 5 1
10% NaOH
(&"OH
l
A
('74)
cCH=NClH
(175) Fe(CO)s
Fe(CO)s OMe
f
OMe NaCN HZ0
(8F,)-
&
l
I &
C.
:
CN
43%
80%
Amines
(S)-Glutamic acid was synthesized in 100% yield and 10-46X optical yield from methyl acrylate,sodium
A-bis[N-salicylideneglycinatolcobaltate(III)
and sodium A-~CN-3-methylsalicylideneglyicinatolcobaltate(IIi) 'Diastereomeric complexes were formed and electrochemically
Styrene,
l-octene
N-alkylaziridines followed C543J.
and cis-2-octene by treatment
by an oxidative Olefins
were converted
at pH 11.4.
reduced [542].
to the corresponding
with a primary amine and palladium
cleavage
were diaminated
(Br2)
of the a-alkylpalladium
by osmium-imine complexes
(eq.
chloride
complex 176) C5447.
Primary and secondary amines were converted to secondary and tertiary amines by alkylationwithalcohols and Raney nickel (eq. 177) C5453.
in the presence of tri-t-butoxyaluminum a-t-Butyloxy- and a-acetoxyacrylonitriles
were converted to imides upon treatment with ferric chloride in acetic anhydride
References
(eq. 178) [546].
p.303
286 \’ -
1) CClL 2) LiAlH,+, 3) i&O
-I-
P R
Et20
(176)
l
or
2
76% R' = H
63%
'
RI,
(tBu0)9Al RaNi
R30H
f
R2' R1 = ph-
89%
R = n-octyl.
CdoPMe
NH
, R'=H
R = R' = n-Bu
/4'+,+
+N
Me0
R=Ph
//N-t
0\
R2 = H, Me;
Rl 'N-R3 R2'
'
(177)
34-98%
R3 = n-pr.i-pr
-;CH2)5-
CN
’
OtBu
NC
(EtO),;' 'OtBu
l
FeCl? Ac20
I x R
l
R
(178) n
NH
Me
D.
Ethers,
Methanol
added
acetylacetonate,
in 98% yield. c5471.
1,4
sodium
to methacrylic hydroxide,
of a platinum(I1) conditions
by potassium acetate
esters
in the
triphenylphosphine
presence and
of
(eq.
acetylated olefin
179)
complex
CSL.87.
peroxydisulfate/acetic
complexes
as catalyst
alcohols
was
The
in 50-100X
as catalyst mechanism
acid studied
with
nickel(Ii)
triethylaluminum
With base but no nickel salts, only 30% yield
N-Acetylimidazole
sence mild
Esters
was
yield
in nonpolar
of aromatic
obtained
in'the media
preunder
acetoxylation
2,2'-bipyridine/palladium(II)
[549].
287
R’ (CHz)n-;-OH
+
PtC1T(C7H~) 3
N-acetylimidazole
ril
(179)
R’ n = 1, 2, 3, 6
-;OAc
R = H, CHs
RI
R’ = H, CH,
50- 100%
E.
Heterocycl es
Two new approaches
and isoquinolones
to the synthesis
esters
produced substituted
2-acetonylbenzoic
sodium hydride
in t-butanol
Alternatively,
reduction
(eq.
180).
P-bromobenzoic
acids
acids _
Cyclization
sodium carbonate. upon reaction
esters.
produced
The other
Isoquinolones
halides
were prepared
lactones
acetylene
insertion
8-methylene-&lactones presence
acid,
and acid
hydrolysis
Oxidative
cleavage
cyclopropanone
chloride
of the copper in low yield
reacted
oxiranes
reacted
reacted
182) [5517.
C5521.
in fair
yield
184) C5.547.
(eq.
Ring openin
of
in the
yield
iron and cobalt
(eq.
catechol
of titanium
185) C5557.
cata7ysts substituted
in refluxing
tetrachloride,
183) [5537.
Mixed silylketals
in the presence
A cyclohexadiene
with copper acetylacetonate
intra-
produced a 6-keto-v-trimethylsilyl
in excellent
while
786) [556].
ides
and carbon
chloride
complex of 3,5_ditertiarybutyl
(eq.
(eq.
The mechanism
alcohols
with carbon monoxide and rhodium catalysts
6 lactones, (eq.
fashion
and
to 2-buten-4-01
with an aldehyde, titanium
with aldehydes
to give y-lactones
6 lactones
catalyst
of
chloride
agent was found to involve
gave pentenolides
chloride
unsaturated
(eq.
during cyclization
which upon treatment
produced a lactone
in a similar
by trimethylsilylmethylmagnesium
of a nickel
carboxylic
by palladium
from acetylenic
monoxide using Pd(PPha),, as cyclizing molecular
of the reaction
were cycl ized
chloropalladate
yield.
to produce 2-allylbenzoic
was effected
carboxyl ic acids
of a-methylene
in excellent
produced the dihydroiso-
approach consisted
to isocoumarins
of substi-
bromide in DMF
Treatment of these with
isocoumarins
hith s-allylnickel
with lithium
of preparation
with n-(E-methoxyallyl)nickel
by sodium borohydride
Unsaturated
181) [550].
dihydroisocoumarins
Treatment of a variety
have been developed.
tuted E-bromobenzoic
coumarins
of isocoumarins,
xylene
of tetraVinyl
to give
e,y-
give a,B-unsaturated diazoacetylacetonate to give
a polycyclic
288
e COOMe
OOMe
k
Br
o
X
(180)
COOH
FOONa
I R * X 0
60-80%
(18’
X also
+
0
PdC12
+
NaH
+ OH 68%
289
RCH=CHCH2COOH
Li7PdC11, H20
0 32-38%
(182)
R RCH=CH-CH2CH2COOH
+
Me7SiCH7MgCJ NiCJ,cataJyst '
Me3Si&ooH
+%j%i=+
95%
\ A
(183)
R
fair yield
(134)
lactone in excellent yield (eq. 187) [557]. Certain hydroxyacid salts of rigid conformation lactonized rapidly in the presence of copper and zinc(I1) salts C5587. Chiral 4-alkyl-y-Jactoneswere prepared from alkenyl g7utamicacidenantiomers by a sequence which involved organocuprate alkylaReferences
p. 303
290
EtG
0SiMe3
X
+
TiCl,
RCHO
-f
l
(185)
Rh(I)
~
75% RI, R2, R'-6 = H R3 = Me
R&
\ 3-
1
+
I
R4
co
~
(186)
R6
R5
R3
1
Fe,Co
RL
R2
R5
f-
'. RQ % R3 = alkyl favors lactone
R6
R5 = COOMe -f loss of CO2
R1, R6 = alkyl + acyclic ketones
tion of a tosylate of the la&one
without ring opening (eq. 138) C5591.
1-Hexyne reacted with carbon dioxide in the presence of Ni(CODj2 and chelating diphosphines to give 4,6-dibutyl-Z-pyrone
in lovtyield C5601.
291 ,OMe
(187)
H 71%
Oxidation
of P-hydroxyalkylfurans
with
pyranones
in high
C.5617.
yield
some
chloro-n-allylpalladium
(eq.
190)
(eq.
189)
chloride
pyridinium Carbon
chlorochromate monoxide
complexes
gave
reacted
to produce
hydroxy-
with
butenolides
C5627.
(188)
RcH2fro oyridine chlorochromate
R = Ne,
n-hexyl,
ACH
(189)
2
CH3
Cl co MeOH/CHZC12 8 hr
Ph
Ph h
'
Ph
Me Azirenes acetonate
reacted
to produce
with
ketones
pyrroles
in the
presence
in quantitative
Diphenylazirenes
reacted
with palladium(II)chlo
without
at
to produce
References
catalyst p_ 303
170"
indoles
(190)
\
yield
0
of nickel(I1) (eq.
191)
catalyst quantitatively
acetyl-
[563]. at 30°
(eq.
141)
or C5641.
292
Carbazole
was prepared from phenothoazine
and 2,2’-bipyridyl reacted
in 60% yield
with a catalytic
(eq.
by desulfurization
193) [565].
with (COD)zNi
N-Allyl-2-bromoacetamides
acetate, triphenylphosphine and A similar procedure with TMEDAin DMFat 125” to produce N-acetylindoles. N-ally?-benzylamines Annelated
gave isoquinolines
pyridines
of a,o-diynes
amount of palladium
and nitriles 0
+
in low yield
(eq.
194) [566].
were prepared (eq.
by the cobalt catalyzed cooligomerization Pyridones were prepared in a 195) [567].
Ni(acac):, 25”
R3CHz;-R4
(191) H quantitative
R1 = H3 Me, Ph R2 = Ph Rs = COMe. COPh, CN, COOEt R4 = Me, Ph
Ph Ph
R
Ph
PdC17(PhCN)7 catalyst 30’
(192)
R quantitative
170”
R = H, Me, Ph
similar
fashion
products
from alkynes
resulted
with isocyanates treatment carbanions
and isocyanates
from treatment (eq.
197) [569].
Isoquinoline
of P-bromobenzaldehydein the presence
condensed with silyl produce a-lactams were aminated,
(eq.
cyclopentadienyl
then oxidatively
cyclized
The same
cobaltacyclopentadiene were produced by
oximes with stabilized
bromide (eq_ 198) c5701.
in the presence
in 40-90% yields
approach to 0-lactams,
196) [568].
N-oxides
or -acetophenone
of copper(I)
acetals
(eq.
of the intermediate
of titanium
199) [5717.
iron olefin (eq.
Imines
tetrachloride In an elegant
cationic
200) C5721.
complexes Copper(I1)
to
aBr +BFcoone +
~>cooMe
NHAc
N AC
CCOOMe 25 Pd(OAc)? 2 Ph,P TMEDA 125=‘, DMF
73%
AC
also
(194)
Ph f
/--=CH
7
cpco(col high
’
(car
l
di 1 ution n = R =
n-Bu,
3, Ph,
4,
n = 3,4
5 Ye,
(195)
CH20Me,
COOEt,
CH2COOEt,
CH2CH2CN,
C,F,,
t-Bu FooEt
with
References
R = CH2COOEt
p. 303
and
excess
RCN
-f
294
acetylacetonate type
rearranged
B-lactams
(eq.
penicillin
type
C5731.
201)
to
B-lactams
cephafosporin
R R’
+
RC-CR’
i = Ph,
R”NC0
Me,
R’
= COOMe,
R”
=
“Co catalyst” PhH, 135” 2 hr
nBu, H,
r
+ 0
(196)
H Ph,
Me
R’
Ph , Me , nBu
R5NC0
-
(197)
R4
40-80% (from
alkyne)
same
NOH
R’s
+
as
in
eq.
R2CH,COOEt
196.
NaH/CuBr/Ph:i
(198)
R’ R3
R1 = t;,
Me
R2 = COOMe,
COMe,
R3 = RL’ = H , 0-CH2-0
COPh ,
COOEt , CN
295
R’CH=NRz
,0R5 R3R4C=C ‘OSiMe3
+
R1 = Ph,
i-Pr,
R2 = Ph,
PhCH2, Me
TiCl, CHzClz
base
l
(199)
l
Et
R3 = R4 = Me,
40-90%
(CH 2 ) 5
R5 = Me
CCpFe(C0)2((7’
+
-25”
PhCHzNHz
r
/ 1 PhCHzfH2
1) Cl?, -78O 2) Et3N
\ FeCp(CO),
C”3
(200) and
A
9’3
*
(CH24,
Chlorodibenzofurans with
palladium
acetate
densation
of
223”
202)
(eq.
cyclohexanone steps
Refuel;ces
iodoarenes C5757. in
e-methylfurans
unsaturated
p. 303
were
cyclic
the
formed
[574]. with
by the
Dibenzofurans
presence (eq.
were
of
203)
to
The iron
butadiene
diphenylethers
formed
by the
by copper
condensed
(MeO)sPCuI
[,576].
from
of
also
2,4-dimethoxyiodobenzene
Diazodimethylmalonate
peroxides
cyclization
after
catalyzed
produced
furans
powder
at
enol ethers of
with
produce
con-
several
other
decomposition in
high
yield
of
296
(201)
THF
cu(acac)7
F 43%
(eq.
204)
with
a,a’-dibromoketones
route
to
t-5777.
muscarines
cyclization in
high
Diiron enacarbonyl effected the condensation of amides
of yield
tyiacetone
1,4-diols [579].
via
to (eq.
produce
205) to
furans,
A bridged
a platinum
Palladium
chloride
and 1 ,Spentanediol
bicycliz
complex
This
3(2H)-furanones.
[5781.
(eq.
triether 206)
was used as a catalyzed
to
the
tetrahydropyran
was produced
from
ace-
[580].
OMe
OMe
HBr
Cu powder 220°
ile
+
N2C(COOMe)2
+
(MeO)aPCuI
-
Me
(203)
1) NaH 2) LiAlH, 3) H+
‘0 +Ir? 72%
e ‘.
297
I
crc;“:
I
IO
NO
FeS04 aq. THF
’
\
\
\
quantitative
(204)
Br
Br
0
R '_ Fe3(C0)k
l
(205)
NMe,
R = Me,
Et,
i-Pr,
R’
Me,
Ph
= H,
+
t-Bu
30-90x
K2Pt6rL
-
--
NaCN
References p. 303
KOH
O\
,CH(COCH,),
O/ptNCH(COCH,),
+
HC’
(206)
298
Imidazolones chloride aniline
assisted
and iminoxazolidines
were prepared
reaction
with a-aminoesters and 2-hydroxyr-Allylpalladium chloride reacted
respectively
with 1,3 dipolar
(eq.
f
297) C581].
by the palladium
species
Ph&N=N-Ph tc give both the dimer and the ally1 The ally1 adduct was thought to occur via species.
adduct of the dipolar
+-NC
of isonitriles
PdCl 3
R’CHCOOEt
(201
N-+
AH2
R’ = Me (42%);
PhCH2 (80%);
i-Pr
(82%);
set 5u (70%)
+
-f
also
+
-/-NC
+
Ag,O
PdCl,
84%
generation
of ally1
cycloaddition
chloride
followed
to the palladium
by cycloaddition,
complex itself
cycles were available from the intermediate isonitriles with dicobalt octacarbonyl (eq. dimerized other
upon treatment
heterocycles
209) C5841. dicobalt (eq.
Azobenzenes
210).
Yields
[I5821.
than by
A variety
of hetero-
produced from the reaction of 208) [583]. Phenylazirenes
with chromium, molybdenum and tungsten
were available
octacarbonyl
rather
reacted
by slight
variation
with isonitriles
reported
[585-J.
carbonyls.
scheme (eq.
in the presence
to produce 6H,12H-indazoloC2,l
were not
of this
of
,a]-6,13-diiminoindazoll
Oxazoles
were synthesized
by
the tungsten hexachloride decomposition of a-diazoketones in the presence of nitriles (eq. 211) [586]. Isoxazolidines were formed in the reaction of oximes with butadiene 212) [I5871.
and palladium
Reactionsoforganometallic
has been reviewed
(7 references)
[588-J.
nitrate-triphenyl
phosphine
compounds in the heterocyclic
(eq. field
299
NP t
NC
CO2(CO)8+
9o”
‘WCNR)
(RNC) ,Cd
l
Y R/N
R-Q-J\ R = H, R’
= H,
OMe, CHO,
3
M(CO)E, ;“,:
(208)
>
R’
60%
Me C=N-Ph also
(209) tiHo
-
s
80% ‘0
67-863
?
Ph
(210)
X NR References
P_ 303
Miscellaneous
H.
Allylphenyl and benzylphenyl Ethers underwent carbon-oxygen bond cleavage
upon treatment
zero
Similarly,
and Ni(PEt,),C5897. SiMes,
with
valent para
nickel
complexes
substituted
(H,
Br,
CMe=CH2, CH2CH20Ac, COOMe, CHOAcCHs) benzylallyl
N III c
+
such
as (COD)zNi
Me, OUe, Cl, ethers
were
cleaved
(217 1 Irlcl=
R
l
i 50-66% R = Ph, Me, Et,
vinyl
(212)
63%
to
the
corresponding
homogeneous
para
RuC12(PPha),
mixture
of
glyrol
dioxide
and hydrogen
hydrolyzed
lo3
*and cobalt(II), Cyclic
mono-
to
at
lo5
catalysts
(es.
213)
benzaldehyde
as a catalyst and diformates 100”
faster
compared
hydroperoxides
substituted
to
were
c5907.
Epoxides
and 40 atmospheres
the
hydroxide opened
64-83% yield
by RuC12(PPh3)a
when catalyzed
ring
in
[591].
Imidazole
a
esters of
hydrolysis ketones
to
carbon
species
mediated
conjugated
cleaved
catalyst,
by hydroxo ion
to
were
using
nicke7(II) [5921.
by palladium(I1)
C5931.
c% R
Pd( II)
OOH
+
(CHz),,
R=H
n = 1,
R=Me
n=2,80%
75%;
n
2,
50%;
n = 3,
35%;
n = 4,
20%
HZ0
(213)
301 Dimethyl
diazomalonate
copper
salts
chiral
sulfoximines
were
to
replace
converted
AgTFA,
A and
by treatment
with
cyanates
by treatment
214)
the
115981.
f
R = o-ClPh
Treatment
produced
copper(I)
sodium
Other
asqualene
to
Ph
with
be a good
solution
iodide
were
prepared
in the
carbonate
allylic
to give
alcohols
RNH-C-NHR
also
(214)
EiTs
(57:;), cyclohexyl
anhydrous
procedure
of chiral
penta-
selenocyanate
iron(III)
(66%)
for
in dry
chloride
1,2.5.6-di-o-isopropylidene-o(-D-glucofuranose)
was claimed
iron seleno-
[599].
(86%),
of glucose
or
2-bromothiophene
and
of
to X-tosylimino-
ferric
with
iodide
(Hg(TFA)*,
to aryl
using
Using
synthesis
thiocyanates
in 77% yield.
fashion
o-MePh
and
reacted
1) Cu or Fe(C0)5_ rfx CHCl, 2) aq. HCl
(72%),
100”
at
yield.
salts
of copper
converted
of
Thioesters
converted
by aqueous
sodium
in 40-603
metal
were
presence
15947.
in a partial
presence
HMPT
alcohol
Z-thienyl-CH,CH,CHO
TsNs
with
were
followed
acetate,
in a similar
RN=C=NR
in
group
used
selenocyanates
Ally1
of palladium
aldehyde
reacted
Alkyl
in the
in the
retention
was
iodides
KSeCN
by hydroboration
or thiocyanate presence
with
Carbodiimides
Aryl
with
sulfoximines
by treatment
tosylazide
[596].
C5971.
olefins
went
conversion
B [5?57.
(eq.
as a catalyst
This
with
by the malonate
reaction
AgBF,).
carbonyl
from
oxygen
the
to t-butylesters
CuTFA,
cytochalasins ureas
reacted
acetone
in 82% yield.
making sugar
co, /”
acetonides
was
used
c6007.
as a liquid
This Finally,
phase
CONRh\O
for
the
separation
Quantitative
of the
resolution
two
enantiomers
in 3 hr at 27"
was
of 3-methylcyclopentene. reported
[601].
Reviews
VT _A.
The
following
"Preparations
of Highly
Organometallic "Titanium "Recent
reviews
theses
Reactive
Synthesis"
Metal
in the
have
appeared:
Powder s and
Their
Synthesis"
Organometallic
(59 references)
Chemistry
of Titanium"
C6047 "Low
Valent
References p_ 303
Titanium
Use
in Organic
and
C6021
in Organic
Tetrachloride Advances
and
in Organic
Synthesis"
(thesis)
[605]
[603] (21
references)
302
“Organic
Synthesis
“Organopalladium “Selective
via Metal Carbonyls” Intermediates
(book)
[606]
in Organic Synthesis”
Organic Transformations
(279 references)
via s-Allylpalladium
(-6073
Compounds” (thesis)
t6081 “Organic “Recent
Synthesis
with Palladium Compounds” (157 references)
Progress
in Organic Synthesis
(126 references)
using Iron Carbonyl Complexes”
c6101
“Organic
Synthesis
with Iron Carbonyl”
“Organic
Synthesis
with
“Reactions
[6091
of Olefins
(197 references)
Tetracarbonylferrate”
(43
c6111
references)
[6121
with Palladium and Rhodium Complexes”
(7 references)
C6131 “Organic
Synthesis
“Me’:al-Carbene
Using Transition
Metal Compounds” (19 references)
Complexes in Organic Synthesis”
“a Anions of Metal-Carbcne
(~150 references)
Complexes in Organic Synthesis”
c6141
[6151
(61 references)
c6l61 “Arene-Metal “Organic
Complexes in Organic Synthesis”
Syntheses
via Allylic
(55 references)
[6171
Complexes of Metal Carbonyls”
(300 referent
C6181 “Transition
Metal
“Cyclometallation
Reactions”
“Ortho-Metal lation “Heterogeneous “Catalysis
in Organic Synthesis”
Hydrides
Reactions”
Catalysis:
(133 references)
II6213
Reaction”
(63 references)
(34 references)
“Free Radicals “Transition
in Organometallic
“Catalysis
Chemistry”
(298 references)
of Symmetry Restricted
(93 references)
Catalysis
and Organometallic
(195 references)
C6301
C6267
Compounds” (285 references) Metals“
(156 references)
of Phosphorus Ligands in Organometallic
Homogeneous Catalysis”
Metal Complex
c6251
Metal Complexes of Olefinic
Effects
Transition
[624]
“Organoni tri le Complexes of Transition “Steric
[622]
A Bridge Between Homogeneous and (20 references) c6231
“Development and ApplicationsofHomogeneous Chemistry”
(38 references)
Complexes:
Catalysis”
“How Asymmetry Might Be Induced in the Chiral Catalyzed
[6l9]
[620]
Some Recent Developments”
by Polynuclear
Heterogeneous
(157 references)
(thesis)
L-6277
c6281
Chemistry and
c6291
Reactions
by Transition
Metal Compounds”
303
"Coordination in Applied "Activation "The
of Alkanes
Homogeneous
"Mechanism Metal
Heterogeneous by Transition
Catalytic
of Oxidative
Complexes"
Catalysis"
(49
"Cyclobutadienylmetal
Metal
Activation
of
Compounds"
of Organic
references)
[634] (355
(102
Carbon-Hydrogen
Addition
Complexes"
(90 references)
Halides
references)
C6371
references)
Bonds"
to Group
[632]
[633]
8 Transition
[535]
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T.
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M.
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(1977).
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and
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3759
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TRANSITION ANNUAL
LOUIS
METAL
SURVEY
DERIVATIVES
COVERING
THE
IN ORGANIC YEAR
SYNTHESIS
1977
S. HEGEDUS
Department of Chemistry, Colorado State Fort Collins, Colorado 80523 (U.S.A.)
University
CONTENTS I. General
Comments
II. Carbon-Carbon
187
Bond
Forming
188
Reactions
A. Al kylation
188
B. Conjugate
22c
Addition
230
C. Acylation D. Oligomerization
241
E. Rearrangements
252
III.
Oxidation
259
IV.
Reduction
268
V.
Functional A.
Group
282
Preparations
282
Halides
B. Amides,
Nitriles
C. Amines,
Alcohols
D. Ethers,
Esters,
284 285 %86
Acids
E. Heterocycles
28-i
F. Miscellaneous
300
VI.
Reviews
301
I.
General
use
Cements
annual
survey
of transition
metal
This
It is not
covers
literature
intermediates
a comprehensive
*Annual Survey covering Vol. 143(1977)309-383 References P. 303
the
review
but
the year
for
for
organic
is limited
1976
see
1977 dealing synthetic
to reports
J. Organometal.
with
the
transformations. of discrete
Chem.,
188
systems that lead to at least moderate yields
of organic
compounds, or that
allow unique organic
low yields
are obtained.
Catalytic
transformations,
reactions
that lead cleanly
extreme conditions
are also
The papers in this than by organometallic ested
in the organic
Specifically Also
since
excluded
are
systems unless reports
survey are grouped primarily reagent,since
are papers dealing
structural
The number of papers reviewed reactions, to a lesser
extent,
for
A.
of
synthetic
in this
reproduction
application.
of
since
the
this year is roughly
twice
more efficient
and solid
the growing activity coverage
Finally, patents
reported
are
results.
that of last
in the areas of carbon-carbon
reflects
series.
organometallic
bond forming
phase
supported
in these areas and,
of the literature.
Al kylation
Organocuprates of a variety
continue
natural
to be extensively
products.
discrete
Subsequently,
of lithium
by IH NMRand molecular
existence
methylcuprates
association
of LiCuz(Me)z,
In general
solvent
CZ].
borane resulting
tyl ides,
ha1 ides
reacted
propyl
with
a variety
Cyclopropyl
by treatment
cuprate
3).
[IS].
product
phosphine.
while
4) El.
vinyl
cuprates
from trimethylsilylacewith retention
Similarly,
2) [4].
lanes
of conA cyclo-
rem dihalocyclo-.
This procedure
was.used
to synthesize
An asymmetric cross
coupling
of phenylmagnesium
was effected
using nickel
The use of the (R)(S)ohosphinegave
theuseofthe
Cl].
Li2Cui4e3 was most
by RX (eq.
was claimed as an intermediate. (eq.
solfor
to produce trimethylvinylsi
with BY,CuLi followed
bromide with 4-bromo-1-butene ferrocenyl
of
bromides were alkylated
propanes were dial kylated and sesquicarene
in ether Evidence
Trimethyl silyl
formed by exchange with the vinyl 1) C37.
data.
LizCuMea and LiJZu,Mes with alkyl,
ha1ides were studied.
and THF was the superior
figuration
the a?kylation
of LiCuzMea and LizCusMes was obtained
the reactions
cycloal kyl and aryl
(eq.
for
substrates, with much activity in the development to the synthesis of reagents , and their application
The composition
vents was studied
reactive,
exploited
of organic
of new organocuprate
(eq.
metal catalyzed
survey
studies
it.
Carbon-Carbon Bond Fonning Reactions
II.
the
with transition
asymmetric homogeneous hydrogenation This increase
type rather
to be more inter-
have not bee? surveyed
to allow
with most of the increase
by reaction
is likely
by another
data useful
literature
detailed
catalysis.
and do not involve
than the metal causing
and mechanistic
they present
sufficiently
year,
the reader effected
these are covered
from the patent
rarely
to a major product
included.
transformation
excluded
hydrosilation,
even if
(S)(R)
phosphine
produced
chloride 34%eeof
34%eeof
sirenin
and a chiral the(R)
the (S) product
189
RCsC-SiMe3
+
(cyclohexyl),BH
R
SiMe,
H
B(cyclohexyl)2
+
(1) R
X
SiMe,
-
H
P(OEt)q HMPT '
-
R'X
CU
R = m-C6H13-, -(CH,),~THP, CH,OTHP R'X = MeI, ally1 X, etc.
;', $-,CuLi ~
R2
R3
(2)
R3 RX =
RI = H, -(CH,),-
Nr3
MeI,
wBr,
R2 = Ph, H, cyclohexyl, PhCH20CH2 BrCH2COOMe, n-CfiH176r
R3 = H, Ph, Me R'+ = H, Me,IVfi CH3
X
X X
Cu-Li
Rl,CuLi
t
61
R
R2
cu
R R1
2+-
R = Ph, n-hexyl, PhCHzOCH2 R1 = n-Bu, s-Bu, t-Bu R2Y = MeI, EtI, CH,COBr, EtOH
References
p_ 303
Rl
R2Y l
J+ 60-90:
I90 Cl
Cl 1) (tle?C=CHCHpCH,& CuLi 2) Me1 3) H2S04-Hz0
ti
OuO
I
I 0
?Q
44% (3) NaH (MeO),CO
-
d,l sirenin
l
MeOOC
CHz=CH(CHZ)zBr
+
d,l sesquicarene
--
PhMgBr
+
NiClz
f
*P
Et70 r rfx 46 hr
CHz=CHCHMePh
(4)
16-58% yield 34% ee
iPha (R)(S)
or
(S)(R)
The alkylation of o-bromobenzoic acids by stabilized enolates was accomplished C71.
in
high
yield
using
sodium
hydride
and
cuprous
bromide
(eq.
5)
Terminal arylacetylenes were synthesized by coupling -in situ generated
72% COOEt
COOEt ,
RiH ;OOEt
,
also work.
and 0
copper acetylides with aryl iodides (eq. 6) [IS]. Vinyl zircona&, hydrozirconation
from
of alkynes, were coupled to aryl halides to produce styrenes
19: using a nickel(O) catalyst. internal
TMSCECCU
only
Terminal alkynes reacted in high yield 35% yields
?I BuLi 2)
HC-CCH(OEt)2
and
ArBr
Br
ArX
gave
alkynes
(eq. 7) 19-J.
In a similar
while
fashion
ArI
(6)
PY
failed.
I
=
R=H
71%
R = p-Me
45%
R = m-Me
50%
R = p-OMe
50%
R’
H
H
ArX Ni(0) cat.
R’CXH
(7) H
Cp,ZrCl
Ar
75-992 R' = n-pentyl.
EtO,
n-Bu,
THPOCH,CH,-
Tolerates COOMe
unsymmetrical L,Ni
biaryls
or LzPdClz
or magnesium
halides
symmetrical palladium nesium lyzed
failed
nitro,
[12].
(BrZnCHzCOOEt)
methyl-, copper(I)
with
iodides
by treatment
phenyl-,
benzyl-
salts.
Use of
trialkylboranes
with
tetraalkylborate
to replace
complete
retention
p.
303
the
with
iodides
and
CN and
group.
yield
by the
or benzyl
halides
acetyl
with
by the
aryl
mag-
palladium(O) at
100".
groups.
were
of the
Un-
in 80-92;; yield halides
zinc
cataThe
Chlorobenzene
prepared
Reformatsky
by the reagent
[13]. with
retention
n-butyl-,
led
with
of stereochemistry
i-propyl-.
reagents
with
the
stereochemistry in the
to polymers
followed
reacted
of
n-pentyl-,
or allyl-Grignard
halide
aryl
by the
acids
coupling
vinyllithium
These
aryl
phenylacetic
alkylated with
of aryl
o-methyl
methyllithium
salts.
acrylate
Rderences
aryl were
prepared
coupling
catalyzed
in high
with
were produced
chloro,
Finally,
or paliadium(0)
yield
were
of allyl-tri-n-butyltin
to react
Vinyl
cross
prepared
halides
OMe,
homocoupl ing was observed.
fluorine
Allylbenzenes
tolerated
nickel(O)
50-702
catalyzed
[ll].
were
of aryl
Very 1 ittle
containing
chloride
reaction
diarylmethanes coupling
[lo].
biaryls
halides
reaction
and
catalyzed
Cl,
on aryl
by cuprous
cis
alkyl
Cl57.
(not The
the
presence
1141.
of
produced
copoer-
&branoethyl
methyl)
reaction
of
Treatment
iodide
and trans
in
t-butyl-,
of
group
with
e-haloenones
192
with
a a,o-bis
1,4iaddition
cuprate
duced by treatment reacted
led
and alkylation
with
of the
alkynyl
produce ene-ynes
zinc
to the
bis
cuprate
+
Ia
of Spiro
(eq. with
8)
compounds by combined
[16].
acid
Diketones
halides.
in the presence
halides
in high yield
WC1
production
of a halide
Vinyl
(eq.
catalyst
to
9) [177.
O
-
RvR
halides
of a palladium
and high stereospecificity
R
were pro-
-A&
U
R
60%
Ib I
Li(L)Cu-(CR,),-Cu(L)Li Ia Ib
n=4 n=5
R = H, Me
R
(8)
&R 40%
60%
x
R!
RI
P3 +
R=
Cl ZnCXR4
P3
+X
5% Pd cat. O-25”
-
(9)
R’
X
X = Br, I
CaCR4
-80% yield
R1 = H, n-Bu, R2 = n-Bu,
COOMe
H, Et,
297% stereospecific
Me
R3 = H R& = H, n-pentyl,
Aryl
and alkyl
in the presence with y&
n-Bu
Grignard
reagents
coupled
of Ni(Ph2P(CH2)sPPh2)C12 (eq.
bromotrimethylsiloxyalkenes
a nickel(O)
cleanly
catalyst,
was also
produced by treating
with
&b’romovinylethyl
10) Cl8-i.
A similar
successful
[19].
nickel
ether
coupling
Finally,
bromide with butyllithium,
193 promoted the reaction between lithium ester enolates and vinyl halides (eq. 11) c207.
RMgBr
+
Ni(diphos)Cl,
BrCH=CHCEt
+
RCH=CHOEt
(10)
53-773
(711
with
LiCH,COOt-Bu
Phi
73x BrW
ggz Br
PhBr
94%
41%
olefin stereochemistry maintained
A T
60%
phASr
B3Yi
Sr
LiMeCHC02t-Bu
+
53x
B*
LiMe2CCOOEt
+
Liw LiPhCHCOOEt
+
Allylic alkylating
Phi
produced
CHz=CH-, ofallyi
isomers
halides
were
complexes quinones
+
Sr n
with
bis
ketal
methyltrialkylborate
was
salts
complexes,
Hith
borates.
observed,
allylammonium
presence
of copper(I)
of the
complete
agents
465
while
3-chloro-
propargyi
reacted
with
haiides
a variety
Ph, PhCH2, Me(CH2)7C=CH2, MeCH =CHCHp,
displacement
alkylated
quinone
alkyl,
in the
as alkylating via
transposition
(C2-7
HCXCH,) with
by copper
or 5-chloropentyl
Quaternary
[Zl].
reagents
HC-C-,
alkylated n-octyl,
allylic
aiienes
of Grignard
were
n-hexyl,
1-phenyproo-1-ene,
COOEt
46%
halides with
72::
Bw
[23].
salts
trialkylamine
allylic A very
alkylation
group
rearrangement neat
has
mixtures
[22].
Allylic
using
synthesis
recently
to give
of
been
RCu.SFs
isoprenoid
developed
(eq.
12) 1247, and involves alkylation of a vinyl cuprate. a-Bromoacids and esters were cleanly alkylated by methyl, ethyl and isopropyl ctipratesC251. Tricyclo[3.1.1.03~6]heptan-6-yl produced
in the
reaction
8’ tetrabromoacetone were
alkylated
References
p. 303
derivatives
of cyclopentadiene
(eq.
by n-heptyl.
13)
1267.
n-butyl
were
prepared
iron
tricarbonyl
B-Bromoethers, and
cyclohexyl
from
acetates Grignards
compounds
with and
CL,U',S, alcohols
in the
presence
prenyl
92%
geranyl
96%
phytyl
93%
0 + Br,CHF-CHBr2
---f--f
-
Fe(W)3
(73)
of 5% cuprous
iodide.
t-Butyl
Grignards
failed
acetates but reacted well with the alcohols
[27].
to react
with the ethers
and
The chromium tricarbonyl
group was used to both activate and alter stereochemistry in the alkylation of arylacetic esters Alkylation of cyclic
by phase transfer catalysis and sodium hydride. ester complexes is stereospecifically exo (with respect
to the Cr(CO)s group)
while
acyclic
stereoselectivity
(eq.
benzylic
a-haloketones
dienyl
halides,
14) 1281.
analogs Finally,
undergo alkylation cyclopentadienyl
and pyrylium
with less
copper al kylates
ion to introduce
a cyclopenta-
group C29-J.
Several new methods for the conversion of acid halides to ketones have been devel aped. The rhodium(I) complex L,Rh(Cl)CO was anchored to a phosphine containing
polystyrene
to produce the alkylrhodium(1)
resin,
treated
complex,
with n-butyl
which then reacted
or phenyllithium with an acid
195
olof,,,
Cr(CO)F, r
m"Me
P&C r
Cr(COjs (14)
OMe
Also
3 03 \
&,$
studied:
COOMe
RX = MeI,
halide
BzBr,
to
produce
supported
ketone
system
ly reported and
both
Br
e
was
Only
n-hexyl. ketones
were
by Z" alkyl
purified
reacted
in 75-92X yield.
The
one
the to
with alkyl
of the
prepared
aroyl groups
with
RCOCl
-I- R'R"CHCu
7
0
and n-butylacetylenewere
Ally1
L,PdC12
ketones
and
were
allyl-trimethyltin alkynyl
ketones
manganese(I1) aldehyde
ReGxencesp.303
acylated cuprous
prepared with
were
and
ketones
were
resulting
with
a variety
catalyst
[313.
ketone,
and
15)
of acid
as a catalyst treatment
underwent chlorides by the
competitive were
reaction
amine
[34].
of acid
Phenyl
F1 /R' R-C-C-R" A#,.
_
acid
c331.
with
alkenyl
and
with
organo-
alkylation
polymerized
16)
halides
Alkyl,
(15)
by treat(eq.
chlorides
of acid
halides
alkylation
[32].
halides
in triethyl
and
Ditertiary
of acid
R,"CuLi
by treating
methyl-
i-butyl
I&
by the
acid
f
lower,
alkyl aryl ketones
alkylation
(eq.
R' 0 " / RC-C-R"
+
in 37-86": yield
produced
the
previous-
were
n-butyl-
transferred
alkylcuprate
iodide
Aldehydes
conjugated
groups
of the
ClRh(PPhs)s
prepared
iodides.
group
Symmetrical
to produce
This
the
Copoer(1)
[30].
n-propyl,
R' LR"
filtration
involving
than
the yields
chlorides
a different
R-;-CH'
although
were
complex.
to use
used
alkyl
bromination
cuprates,
a-haloketone
with
by simple
three
chlororhodium(1) convenient
system,
by a sequence
of the
ment
starting be more
homogeneous
were
trialkylborates
and
claimed
identical
systems
, HC-C-CH,Br
at the
C351.
chlorides
with
196
0 R+CH
+
0
LpPdClT/ CuI,EtsN
R2;-Cl
k
RIC=C-t-R2
(76)
60-961 RI = Ph,
n-Bu
R2 = Ph,
PhCH=CH,
- Fez(CO)s this was
in refluxing
reaction used
coniums, acid
formed
does
n-octenes
react
+
, NMe2
olefins
Fes(C0)12,
Transmetalation
with
acid
a rapid
acid
Cp2Zr(H)C1
and
from
chlorides
hydrozirconation
give
with
Fe(CO)s,
[36-j.
by the but
i-Pr,
ether.
to occur
to acylate
chlorides
which
t-Bu,
(eq.
of olefins,
transmetalation
Co2(CO)a
zirconium 17) are
[377. not
to aluminum
do not
cause
to aluminum Alkyl
reactive
zirtowards
trichloride
chlorides.
+
Cl Cp,Zr-n-octyl
AICll o0
+ Cn-octylA1C127,
CH2C12 (17) 0 R'COCl
l
R:-n-octyl 98%
/c s
EtooC\C’CooEt +
LizPdCl,
+
NaCH(COOEt),
THF ZSO f
/ ‘r
SjPd\
A (NMe)z
(18)
91%
1) LiTPdCIL, 2) NaCH(COOEtj2 31 Hz
(191
f :::::\N, 90%
\
1) Li7PdClr, 2) NaCH(COOEt)2 '
b
Pd-N
(20)
0
l
2:l DMF-PhH
0A
EtOOC
\
COOEt
Cl
COOEt
-
-
Prostaglandins
35% overall from
References
r. 303
0/ \
The
direct
by several
alkylation
palladate
and
stabilized
complex.
The
organic
(eq.
18)
fins
failed
enolates
amines
to alkylate.
led
was
alcohols
(eq.
19)
This
C391.
prostsglandin olefins (eq.
precursor
could
21)
(eq.
be alkylated
[41]
or
ethers,
successfully
Fe(CO),
was 20)
used
22)
and
carbanions
ole-
ketone Homoal lylic carbanions
synthesis
using
full
simple
by stabilized
elegant
appropriate
The
[42].
reported chloro-
borohydride
and
alkylation.
alkylated
Under
by stabilized (eq.
than
in a very
[40].
sodium
esters
organocuprates
rather
been
lithium
o-alkylpalladium(I1)
with
conjugated
reagents,
has
with
a stable
by reduction
of palladium
chemistry
carbanions
reacted
to produce
and
amir-tesand sulfides were also
soft
sulfides
freed
Grignard
to reduction
with
and
carbanions
ligand
Ally1
C381.
of olefins
Ally1
groups.
of a
conditions
simple
palladium
chloride
experimental
details
of
COOEt R COOEt +
H2
PdCl,(CH,CN),
+
f
2 EtsN
+
/
LiCH(COOEt)2
(21)
COOEt
j3-elim. \
R OOEt
II
-Fe(CO),
the
+
1) TFA 2)
EtCH(COOEt)z
(22)
68X
addition
olefin
of stabilized
complexes
cation
ed 1437. cuprates
The and
paper ylids,
allylpalladium (eq.
THF o0 b
cH(COOMe)2
23)
of key
covers and
complexes
[44].
A series
intermediates
reactions
studies
carbanions
to
produce the
has
to cyclopentadiene
stable
addition
extensive
in allylic
of enolates, tables
by stabilized of new
a-al kyl iron of data.
carbanions
n-allylpalladium alkylation
have
has
iron
enamines, The also
complexes been
dicarbonyl
complexes
have appearGrignards,
alkylation been for
synthesized
of TF-
reported use
as models
and
their
[45].
COOEt (Pd<>
2
+
CH(COOEt)R
(23)
' EtOOC
i
COOEt R = CN
Me7S0 THF
70%
R = SO,Me
52%
R = COOEt
quantitative
199 Palladium catalyzed fins
in the presence
Acetylene
reacted
and palladium onitrile,
Iodoferrocene
of palladium
cyanide catalysts
gave mixtures
of both positional
went Mith methyl vinyl moderate and side was phenylated in the presence arylation
resulted
[47].
as a mixture
The reaction
to arylation
but
The reaction
also
oxide, but yields were only The dimethylacetal of acrolein acetate
and tri-o-tolylphosphine
of the dimethyl
of acryl-
of the olefin
isomers.
with bromobenzene using palladium(I1) of triethylamine
iodide
with bromobenzene and
and geometric
ketone and mesityl
products
of copper(I)
acetyl ene C461.
led predominantly
of ole-
to produce al kenylferrocenes.
in the presence
and methacrylonitrile
palladium(I1)
continue
with a variety
was reacted
acetate
with iodoferrocene
to produce diferrocenyl
ally1
and arylations
“Heck” type alkylations
to be used synthetically.
acetal
as a catalyst
to give
of cinnamaldehyde
up to 98%
and methyl-
2-phenylpropionate C49]. Styrene was converted to trans 902 yield by reaction with methyllithium using Pd(scac)2 reaction such
consisted
of a cis
addition-cis
a-methylstyrene in as a catalyst. The Substi tuents sequence.
elimination
as p-C1 (90%)) m-Cl (80%) and p-Me(60Z) were tolerated,
as sodium diethylmalonate,
[49]_
Kinetic
studies
sence of palladium(II)
only a low yield
on the arylation acetate
of
to form trans
of ethylene
carbanions
alkylation
of styrene
(a)
such
PJas observed
by benzene in the pre-
stilbene
mation of a u-complex was the rate limiting step EOI.
were formed by the reaction
but p-OMe sub-
With stabilized
stituted styrene led to low (15%) yields.
with thiophene,
indicated
that for-
Vinyl heterocycles furfural and furan
in the presence of palladium salts [51]. Vinylidene chloride reacted with isobutene in the presence of palladium(I1)
ArNHz
-f
r
+
Ph
ArNz +
olefin
+
Pd(0) cat.
-+
Ph
(24) 57%
References
p. 303
200 acetate
at
in GO%
yield.
60”
to oxidatively couple, producing l,l-dichloro-4-methylpentadie Nitrite was found
to suppress dehydrodimerization
of iso-
butene r-521. Palladium(O) complexes were used to catalyze the arylation of olefins by qromatic diazonium salts.
Ally1 alcohols led to phenylalde-
hydes (eq. 24) C537. Styrene was also directly arylated by anilines to produce stilbenes using palladium(I1) acetate.
The reaction involved C-N bond cleavage [54].
by using a chiral copper complex to catalyze the decomposition of alkyldiazoacetates,
trans-e-menthyl chrysanthemate was prepared in 72%
yield and 94% ee (eq. 25)
C551.The
bulkier the alkyl group of the diazo
,COOR 7.4% cis 89.9% trans d
94% ee(25)
2.7% trans e R = 2,3,4-trimethyl-3-pentyl
Rz = 5-t-butyl-2-octyloxyphenyl
catalyst =
@CO'"""
+
O/CH?COCOOEt
76%
Rh,(OAc), / NzCHCOCOOEt
+ 0
(26)
I
0
07
COOEt 79%
compound, the more trans the trans
isomer.
tuted olefins complexes
product
was formed,
Cyclopropanation
in the presence
reactions
and the higher was the ee of of diazoalkanes
and absence of nickel(O)
of the type M(Me3CNC)2or M(PPh3)2(CzH,)
with substi-
and palladium(O)
were studied
and inter-
mediate complexes were isolated and characterized by x-ray crystallography The reaction of ethyl diaropyruvate with cyclohexene Produced drast567. tically
different
products
when Rhz(OAc),
was used as a catalyst
than Ti-allylpalladium chloride (eq. 26) C57J. Olefins were alky?ated by isonitriles via s-allylpalladium
rather complexes
Isonitrile complexes were intermediates or a-alkylpalladium complexes. a,B-Unsaturated chromium carbene complexes underwent 1,4(eq. 27) C583. alkylation by enolate anions (eq. 28) C591. The role of puckered
\ 0
PdCl 3 h
OPdp
.+
(==+=N-t,u
(27)
MeOH NazCOs ’
Cr(CO),
f
MgBr
CH90S07F >
(C0)sCr !l%
metallocyclobutanes of cyclopropane
(from metal carbenes
formation
was studied
and olefins)
by the --in situ
OMe
in the stereochemistry generation
of
(CO)sWC(Ph)H c601. The [2a + 2x1 cycloadditions catalyzed addition
by palladium(O) products
Referencesp.303
of methylene
cyclopropane.to
alkenes
complexes were found to give mixtures
and cyclodimerization
products.
Unstrained
of cyclo-
olefins
and
202
0 Ce
(CO)sCr
Me0
4+
*
(28)
% 73%
p\&?sL
79%
*.
+&)
I
40%
OMe
20% 82%
l- or tion
P-alkenes metal
were
catalysis
K
unsuitable has
(eq.
29)
Olefin
insertion
in transi-
been reviewed [62].
recently
Pd(0) cat. loo0
-i- RCH=CHR'
1617.
~
R
+ p
(29)
23-94% O-782 The
effect
of solvents
and
lithium
salts
on the
addition
of
lithium
alkylcuprates to l-alkynes to produce lithium vinyl cuprates has been studied in detail.
Lithium
dibutylcuprate
at
greater
than
C-2
the
with
regioselectivity
without
was
addition. were
than
stereospecificity
98%
prepared
by treatment
succinimide chemistry
was
was the best was
for
duction
of
complexes [67].
The
chemistry used
bromide
from
by the
and
group
terminal
C641.
90% yield
[RCuSr~Mg! N-bromo-
the
study
found
that
Vinyl
greater
iodine,
Essentially
it was
alkyne
1631. and
alkyneswith with
In a general
C651.
alkynes,
the
deprotonation
than
of terminal
30)
[IRCuIlLi
deprotonated
vinylcuprate
(eq.
phenylacetylene terminal
branched transferred reaction of addition
in a synthesis
this
1-octyne
with
same of the
CRCuBrlMgCl
for the introduction of 1" alkyl (R) groups into ace-
reagent
other
simply
in greater treatment
and
In contrast,
R2CuLi
thus-formed
by another with
to phenylacetylene
suppressed
alkynes
of the
reported
propyne
best
In THF
or N-chlorosuccinimide
reactivityof[RCuYBgX
tylene,
added
regioselectivity.
lost.
Lithium
bromides
followed
90%
chain only
(forming
alkynes. alkyl
groups
one
R group
of eneynes depended of myrcene
with
[66]. and
nature 31)
Ct-BuOCuRlMgX
good
for
It was
that
RzCuMgX
more
was of R.
C687.
while
particularly
were
CRCuY7MgX
on the (eq.
RR'C=CH2)
THF was
found
reactive
also
than
studied.
This
chemistry
intro-
CRCuBr7MgX
The
regio-
was
.
203
R'C-CH t
CRCuBrBgX
R = Et, i-Pr, cyclohexyl, t-Bu, n-Bu R' = Ph, Me, Bu, H
R,C=C-C-CH +
X = Br, I, Cl
>90%
XY = NBS, NCS, I2
[R"CuY]MgX
-
H+
;il
R2C=C-C=CH2 + i,RI,
>9B% stereochemistry
/H R2C=C-CH=C \R" r;,
a
b
R" = 1" al kyl , >95% a R" = t-Bu, 1:1 a to b (31) =-=f -
CuMgCl -
-
H+
90%
myrcene Thereactions of propargyl alcohol with EtCu and with EtMgBr in the presence of copper(I) salts were compared. In ether both reagents added trans to place the metal on the terminal carbon, while in THF, a cis addition occurred (eq. 32) C691. Similar studies were carried out on the corresponding
allenic
alcohol.
The intermediate vinyl magnesium halide was fur-
ther Functionalized (eq. 33) [70]. Cumulenic ethers reacted with Grignard reagents in the presence of cuprous bromide catalyst to produce eneynes (eq. 34) C717. Use of discrete [RCuBr]M complexes led to reductive alkylation. Propargylic ethers, sulfides and amines reacted with organocopper species in an addition reaction whose regioselectivitydepended on the nature of the heteroatom (eq. 35) C721. The chemistry of the vinyl cuprate intermediates was also examined.
ii""
H&C-CH,OH
References p. 303
c)=(E:,oH
(32)
204 RCH, CHz=C=CH-CHzOH OH
(33)
OH
R = Me,
Bu,
i-Pr,
Ph
R'R"C=C=C=CHOMe
i-
10%
RMgX
CuBr
f
RR'C=C-CeCH ; 80-902
[R"'CuBr?MgX
(34)
I RR'C=C-C=CHOMe R,,,
R = alkyl, R',
Ph
R" = H , Me R
RCu
+
R'CrC-Z
-
R'=H
CH
n-Bu 1
Terminal hydroboration catalyzed
chloride, The l-01
were
alkynes with
were
were
lithium alkynols ethylated
R'=H
converted
of the coupled
chloride
and
3-butyn-l-of.
to trans
hydrides vinyl
(eq.
to halobutadienes oxygen
in acetic
3-pentyn-1-01,
by diethylaluminum
NEt2,
disubstituted
followed
borane
n-Bu
chloride
\
, n-Bu , Me
Z = OEt,
dialkylboron
decomposition alkynes
R = Et,
b
-No a
3
Z = SR'
terminal
77-95%
(35) Z
b
a R = n-heptyl.
X
R'
Z
R'
H
-
t
b
alkenes
by
by palladium 36)
C737.
acid
(eq.
using
bis
37)
a
acetate
Styrene
by treatment
4-pentyn-Z-01
54-92s
No I NPhz -
with
and palladium
[74]. and
4-pentyn-
cyclopentadienyl
205 H
R RCXH
-i
R2’BH
R
+ H
H
)_(-
Pd(OAc):, EtsN THF
(36)
H
R'
58-98X R = Ph,
t-Bu,
Cl(CH,),-
R' = CHMeCHMe,
PhCH=CH2
+
R = Ph,
n-Pr,
titanium minal
cyclohexyl,
PdC17, LiCl 02, AcOH
RCXH n-Am,
internal
3-hexen-l-01
as a promotor.
and/or of Jo&
pargyl
alcohols
were
38)
(37)
on alkyne
50-24002
on Pd
Terminal
alkynes
3-pentyn-l-01
acetylenes
trialkylbenzenes
presence
involving
while
Terminal
in the
sequence
PhCH=CHCH=CCl-R 40-60X
ethylation
C757.
1,3-butadienes
k
Et
dichloride
and
Z-methylcyclohexyl
were
underwent
gave
converted
by treatment
to
alkylated
by aromatic of the
bond
trialkylaluminums
C761.
hydrocarbons
triple
ter4-methyl-
(E)-2,4-dialkyl-
with
(N-methylsalicylaldimine)nickel
protection
both
exclusively
Finally,
through
as a cobalt
an
pro-
unusual
complex
(eq.
t777. R2
R2
R3C-C-C2H
co7(co)R
+
R3_C_C-&)H
‘,, \
:
R’
,R’ -
Hf
R3-C=_C-C+ a’ ‘> \ ’ ‘.
RI
; ,to (CO),Co
RI
(CO13
(38) R3-C-C-C-R2
/
RI o,p
\
ratio
depends
on acid
used HBF4.Me20
40%
+
78%
p only
I
OMe Transition The
oxidative
metals coupling
chloride
was
hydrogen
coupled
yield. having
References
carefully very
Substituted two
different
p. 303
continue
to be extensively
of ketone
enolates
studied.
Ketones
well.
methyl
Methyl
hydrogens
for
to 1,4-diketones with
ketones
ketone's coupled
enolizable
used
a single
coupled in very gave
coupling
by copper(I1)
type
of enolizable
in moderate low yield.
mixtures
reactions.
but
to excellent Ketones
the
!east
hin-
Olefins, cyclopropanes, ferrocenyl and
dered 7,4-diketone predominated. ester functionality was tolerated.
Attempted cross couplings gave all
possible products but two different methyl ketones were cross coupled in Intramolecular couplings
moderate yield by using a large excess of one.
of diketones failed except for diacetyl ferrocene [787. using copper
This reagent also coupled
triflate has also been reported.
trimethy7silylenol
Ketene silylenol acetals were coupled to
ether: C79J.
succinatesbytitanium
Similar chemistry
tetrachloride
(eq. 39) [807.
Osmium(IV) salts coupled dibenrlidene acetone to produce a cyclopentanol product (eq. 40) C817, while palladium chloride dimerized ethynyl vinyl ketones (es. 41)C821.
R'R'C=C
,0R3
R1R2C-COOR"
TiCIL, .
(39)
I
R'R2C-COOR3
'OSiMes
73-80%
PhmLPh
+
In
i
K2 OsCl 6
pheH=CHPh
+
(40)
Ph
COCH=CHPh 100%
R’
0 R'CH=CH:-CzCR2
R2
PdC13(PhCN)7 PhH, A
\ 3+
R2
CH2R1
f
0 (41)
OH
R2
R1 = Ph, RZ = Ph, mesityl CH2R1
R1 = Me 3 R2 = Ph RI = Ph, R2 = Ph, Me RI = Me, R2 = Ph, Me, Et
Reduced titanium species have proven useful for the reductive coupling of ketones, aldehydes and diols. in hiah yield
by cyclization
with a titanium species
Large ring (Cl,- C1s) olefins were prepared
of the corresponding
resulting
a,w-dialdehydes
or ketones
from the reduction of titanium trichloride
207 with zinc-copper by this
route
dineopentyl
couple. (i.e.,
ring
cyclic
olefins
1,2-diphenylcyclobutene,
ketone,
to symmetrical
Small
could
87%) CS3J.
adamantanone and dicyclopropyl
olefins
by TiCle/py,
produced
also
be prepared
Ketones,
by reduction
of Tic14 with zinc. The rea-
Unsymmetrical ketones gave mixtures of geometrical isomers C841.
gent resulting
from the reductionof
aluminum hydride
coupled
the appropriate
(61%) and 1,2-diphenylcyclohexene coupled
to give
Benzhydrols heating
a mixture
of cis
were reductively
A variety
1.2-diphenylcyclopropanes
halides
with a reagent
benzyls
and vinyl
dihalides
halides
to the corresponding
of RuCl,(P?ha)s.
products
J@
were coupled
bromides
were coupled
to biaryls
to give
with zinc,L,NiCl,
was synthesized
by treatment
than cupric derivatives
(eq.
coupling
chromium(II1)
chloride
were coupled to biwith VCl JLiAlH;, while
al kenes [881. Aromatic (PhBr,89%, e-MePhBr, 73X, p-MeCOPhBr, 581,
and excess
by copper(I)
Grignard reagent
possible
c861.
of halides.
to the corresponding
e-Me02CPhBr, 831, e-MeCONHPh, 37%, o-tolyBr, treatment
all
coupling
by
pal ladi urn
from benzhydrols
the reductive
Benzylbromides
to dienes
1851.
hydrocarbons
The corresponding
formation
formed by reducing
[87].
were dehalogenated
to 1 ,2-diphenylcyclobutene
and trans
promoted only ether
aluminum hydride
with lithium
1,3-Diphenylpropane-1,3-diol
Unsymmetrical allylic with lithium
diketones
of metals have been used for
by treatment
tetrachloride
(35%).
coupled
to 190” in the presence
and platinum complexes
titanium
including
ketone were dimerized
catalyzed
42) c901.
12C, 2-brcmothiophene,
phosphine coupling
Cuprous
41%) by
in DMFC877.
Pleiadiene of the appropriate vinyl
catalysts
were found
more effective
catalysts for the Ullmann condensation of haloanthraquinone with amines in aprotic solvents cgi7.
Br
1) activated Mg 2) CuBr, -500 to 20”
(42)
l
Br 45% Pleiadiene Diary1 ,
al kynyl , vinyl
and benzyl mercurials
to produce the corresponding HMPAat 50-130”. Em. Similarly, dienes
Symmetrical tion
v;-iylmercuric
by treatment
Aryl mercuric
hydrocarbon
Di2lkylmercurials
halides
dimer by treatment
did not couple
halides
coupled
with BHzCl-OEtz followed
to biaryls were also
and lithium under these
prepared
by treatment
coupled
with LjRhCl in
under these
were catalytically
with rhodium catalysts
(E,E)-1.3-dienes
were catalytically
conditions
coupled chloride
conditions
to 1,3-
in HMPA. [93].
from al kynes by hydrobora-
with methyl copper
(eq.
43).
208 R’
R R&CR’
f
BHzCl:OEtz
-t
(43)
EE
>99%
R = n-Bu, R’ = H 93%
R= R’ = Ph
R= R’ = Et
99%
R = cyclohexyl.
R = R’ = n-Bu
95%
R = Cl(CH2)s,
“Ate” complexes of a variety
were implicated
of aryl
45% R’ = H 71%
as intermediates
copper aggregates
99%
R’ = H
[94].
Selective
coupling
was explained in terms of intraagcjregate electron transfer processes 1957. In the cross coupling
of aryl
reaction
was shown to proceed via Ar,Cus(C=CR)z
II
Q’- ’
cu
copper
species
to form biaryls
”+
with alkynyl
DMF 175” l
CuC-CR
/
copper
_
\
9,
NMez
complexes
clusters,
(eq.
44),
the
which were iso-
C-CR
(44)
Mez
76-92% R = Ph, p-tolyl, lated
2,4-xylyl,
L,3,6-mesityl,
and characterized.
cluster
contains
Selective
exclusively
and one al kynyl ligand Alkylbenzenes palladium
salts
triangular
were oxidatively
in heteropolyacids
by treatment
with palladium of aromatic
as have coupling
ferences)
ClOO7.
Catalytic interesting
coupling
acetate
anilines
acetate
alkylation
coupled [97-j.
occupied
by one aryl
C98-J.
to biaryls Palladium
with
to bifurans
catalyzed
oxidative
been reviewed (88 references)
metal complexes
were coupled
(500 re-
to 4,4’-diaminodiphenyl-
acetates
has accounted
Treatment of an allylic
using 1% Ll,Pd catalyst
60-98:: yields
alkylation
The same chemistry
by treatment
Furans were coupled
anion of diethylmalonate c1021.
because the
[loll.
of allylic
transformations_ of allylic
occurred
copper faces
compounds has recently reactions via transition
Dialkyl
methanes by palladium
cross
4-Cl-Ph.
[96].
dimerization c991,
4-MeOPh, 4-NO,-Ph,
several
with the
and 10% (+)DIOP led to
with 20-37% optical
was used to elaborate
for
acetate yields
(eq.
45)
COOMe
+
cH(COOMe)2
60-9s:; ZO-37% optical yield
0
! --_(46)
@ OMe
ecdysone
SO,Ph I
1) NaH 2 6% L&Pd rfx, THF
B-Diketones acetate via
assisted
a radical
allylic went
to develop
p. 303
[MeCuXlLi
or Sn2' the
were
with
ally1
where
pathways
with
obtained,
alcohols
[106I_
X is methyl,
depending
product
the The
cyanide
on X (eq.
a-alkylation
major
by the
to introduce
reported
acetoxyepoxides. with
COOMe
g!
terpenic
acetate
were
nucleophilic
reacted
was
from
No yields
with Sn2
of a alkylketone References
reaction
acetates
alkylcuprates
synthesized
pathway.
by either
attempt
were
l
(47)
49)
of ketones,
manganese(II1)
acetonyl
reaction
or thiophenoxide In an
ClO71. lithium
A maximum
yield
being
non
the
group, of
di-
of 43X alkylated
7) NaH 2) LbPd THF rfx 49-692
AcO (n = 1,3)
I exal to1 ide (sat., n = 3)
1) NaH 2) 20% L4Pd + HMPA/THF rfx diphos
0 Q
/ -
COOMe 45%
(45)
hum1 ene
ketone,
from a formal
elimination
ment of OH by R in allylic in eq.
50 [1091.
reactions allylic
Similar
acid [lOS].
The direct
replace-
was achieved
by the sequence described
chemistry
was achieved
using
of Grignard reagents transposition
of acetic
alcohols
with allylic
was observed
in this
alcohols,
(Ph,P)2NiC12 although
case [llO].
Allylic
catalyzed
significant l-perfluoro-
al kyl alcohols of the type CH2=CHCHRF(OH) reacted with iodobenzene in the presence of palladium salts regioselectively at the terminal olefinic carbon to give mixtures
of PhCH2CH2CORF and PhCH=CHCH(RF)OH [ill].
reagents
with monoallyl
reacted
phosphates
in the presence
bromide to replace
the phosphate
regioselectively
amounts of allylic
transposition
were noted CllZ].
reacted
under similar
conditions
to replace
Grignard of copper(I)
in 80-9056 yield. Ally1
sulfonium
Small salts
the R2S by the Grignard al kyl
211
[MeCuX]Li
OAc
X = Me
X
0”10
>95%
CN
=
OX
X = SPh
>957' 3
25%
75%
but
(49)
X = Me X = CN X = SPh
1) 2) 3) 4)
R-OH
-
with
OH,
CHaLi GUI R"Li [PhsPNMeTIPh
/--vo",
, PhCHOH,
R2 = BuLi ,
Li 0
on the
transposition
reagents
References
, MeLi,
were
iodide
p. 303
CH,OH
D-
set-BuLi,
PhLi,
EtLi,
BuCzCLi
double
bond,
S
Depending
of allylic
copper(I)
70-95:;
pvH,
CHs
nard
(50)
OH
v
group.
%
substitution were
selectively
(eq.
52)
on the
observed
[114].
(eq.
alkylated Geraniol
51)
[113].
by halides was
varying
Finally,
or tosylates
synthesized
amounts ally1
Grig-
and
in this
manner.
/
\ 40- 90% y i el ds 30: 70 1oo:o t0 (depending on R’s)
Rl R2 f\ I?3
\
MgX RI R”X/CuI
i
R’ ti
R
(52)
CHzOH I
gerani 01 4-t-Butyl
cycl ohexanone reacted
and MeLi-LiCuMe2 in ether than was obtained methylsilanes to give
with MeLi alone
reacted
high yields
Conjugated
also
ethers
effected (eq.
(eq.
55) [118].
aldehydes
to
promote
attack)
[115].
(eq.
to the carbonyl 53) 11167.
activity
con-
Chi ral atertiary center
between a bromoethylacetate
in higher yields
procedure
themselves
ketones _
in the newly-formed reaction
9roup.
and a,E,-(,&-unsaturate
Simple si 1yl enol ethers
the alkylation
attack
Allyltri-
Titanium
betwtzn acetals
to give 2-hydroxy-1.4-di
The Reformatskii
than when the traditional were used
the reaction
and ketones proceeded
amounts of equatorial
in the presence of titanium tetrachloride
by 1,2-addition
54) Cll77.
induced optical
(87-93)
(69% equatorial
with ketones of alcohols
densed with o-ketoesters ketoesters
wi th MeLi-Li Br , MeLi-Li I, MeLi-Li Cl Ok, higher
enones underwent 1,4-addition
tetrachl,oride silylenol
to give
was followed
using zinc-copper cll9].
and
couple
Chromium(I1) salts
of ketones and aldehydes
by allylic
haJides to give homoallylic alcohols. Coupling always occurred at the most substituted allylic terminus. Aldehydes were more reactive than ketones,
213
R 0
0-
’
R&;OR
TiClr, CH$l 2
SiMes
OH
0
/ ox
*
COOR ’
(53)
/ 70:: +A 0
OR2
R’
+
R3AOSiF,e
TiCIL
3
;
Rlwo
(54)
_( OR2 R3
RI
= Ph,
16%;
R2 = Me,
and
While
88%;
/=, Me
865.
7, ’ nPr
70%;
Et
ester
promoted
PhCH=CH-,
and the
many
cyano photo
substrates
tically
useful
reacted
groups
were
reaction
of
gave
ones
are
with
ketones
to
reacted
with
this
References
P. 303
reagent
low
tolerated alcohols yields
recorded give at
in
tertiary low
ClZO]. with and/or
eq.
56
tetrachloride
C=N containing
complex
mixtures,
Cl213.
alcohols
temperatures,
Titanium
C=O and
in
the
Alkylmanganese high
aldehydes
compounds. syntheiodide
yield.
Acid
at
moderate
chlorides tem-
214
Rz
RI
TiClrt CH&l
H70 r
l
R,Si'
0 R = Me,
R2 R3 0
Et
RI = Ph,
Me,
t-Bu
3
77-100% yields
R2 = H, Me
18-60%
R3 = Re, Ph
optical
yield (55)
RIO, ,c=c, YesSiO
0
AR2
f
0
I/
0 -
R3-&-;4-J
R2R30
&-&&;-_O
R'
x
R2 i)H
‘(1
83-88% R = Me, RI = Me,
H
R3 = Me,
Plr
peratures,
ketones
discriminate Isoprenoid
c1221.
at room
temperature,
between
aldehyde
hydroquinones
allyltrimethylsilane reaction
proceeded
(eq.
C1233.
57)
Epoxides using high
yield
amounts tives
in the
weFe
[IRCuCNlLi
reacted
with
with
the
cleanly
alkylated
expected
iodobenzene
of styryl
presence the
rather
yield
inert.
The
with
C1251.
a-Mono were
same
isolated
for
no need
in some
excess The
with
The cases
reagent
reactions
by went
in
Enol esters (acetates)
Cl241.
to produce
styrenes
or a,a'-dimethyl prepared
molecule
quinones
tetrachloride.
was
acetate
in the reaction
complexes.
regiochemistry
and palladium
acetates
the
reagent
and small
or phenyl
by addition
deriva-
tc excess
[126].
Oxidative variety
which
RaCuLi
were
groups
from
of titanium
quinol,
than
esters
and keto
through
salts
and
resulted
of p-tolylsulfonylhydrazones
R,CuLi
optical
Et
R2 = Me,
could
35-68s
t-Bu
phenolic
of natural
low yield.
Several
couplings
products new,
has
higher
to form long yield
been
polycyclic used,
processes
but have
skeletons proceeds been
common normally
developed
to a in
and
are
215
-j$- LOMe
_b’)--y)ob,
WCHO
H
H
45%
y-v
60%
(56) R
R'
R" N CH
Me@’
+-R
NHR” f
R’
CHpOH
‘OMe
95%
Me0
cupc13
PY, 0, *
tMe0 28% corytuberi
ne
(58) References p. 303
216
R' = COOlMe 3 Rz RI = COOMe, R1 = CN, (Worked
for
benzophenanthridines,
, R3 = OMe
75%
R? R3 = -OCHz-O-
85% 91%
R2 , R3 = -KHz-O-
methyl-picene-14-carboxylate,
OMe
also.)
OMe
OMe
OMe tylophorine
sumarized a model were
in eq. 58 [127l,eq.
ogidative
reported
in detail
Nucleophilic accounted chromium ly meta
for
coupling
substitution
of 2,6-dimethylphenol
The
soecifics
by copper
of salts
C1307.
aromatic
several
carbonyl
59 El281 and eq. 60 [129].
reaction
substitution
useful
reacted with
on n-arene
transformations.
with
a variety
less
than
The
chromium toluene
of carbanions
2% para.
Similar
complexes complex
to give results
has
of
predominatewere
obtained
with
anisole
(94-700%
was
bulky.
and
lithiodithiane
used The
to form
This
studied
C7317.
fused,
reaction
copper
meta).
Carbanions
An
Spiro
or copper
particularly
LiCHzCN,
intramolecular
with
powder
version ring
ethyl
resulted
true
when
LiC(CHs)zCN,
and metacyclophane
of N-methylpyrrole
bronze
was
were
of this
u and
carbanion
reaction
(eq.
systems
diazoacetate
in both
the
LiCHzCOO-t-Bu
61)
in the
was
C1321.
presence
B alkylation
of
of the
OR
HO VOCI? Et,0 -78O to +35'
RO
t
HO
(60)
HO
HO
HO \ COCHs
pyrrole
The ratio of isomers (a-
ring.
on the
metal
Grab
used
type
by copper(I) purified
used
material
(eq.
tion
to prepare
tricarbonyl
A!der steric
reaction. hindrance
tricarbonyl bridged References
p_ 303
and
crude
predominated)
chloride
cycl obutenes
was
to
The
reacted
synthon
energy
of the
(eq.
of the
substrate
underwent
compounds
with
dependent
(eq.
(eq.
66)
(eq.
64)
reaction 63)
iron
and
were
worked
65) Alder
[138].
[137].
pro-
cl351. tri carbonyl
by the
cyclobutadiene
than
between
8 la&one
ultimately
generated
promoted
better
was
cis,trans-
oxidation
2,5-di-t-butylbenzoquinones
strained
Diels
promoted
cycl obutadienyl
Cyclobutadiene,
[136].
rings
complex
and an unsaturated
1,3,5-cyclooctatrienes
complex,
six-membered copper
The nickel
C1341.
use as an isoprenoid of
complexes
bicyclic
62)
The
magnesium
a compound of
1 ,Scyclooctadiene
iron
of five-
trifluoroacetate.
Cycloaddi
always
[133].
fragmentations
trimethylsilylmethyl duced
50%
of
overcame
the
Cycloheptatrienyliron
reactions
with
The
palladation
ortho
TCNE
the
in a Diels
to give of
218
1)
43
(LiTMP)
N-Lif
(‘&)&HP
l
THF, -78O 2) oxidation 89%
Q/\
(CHa)&HzCN
dr(CO),
CN
1) O", 24 hr 2) Hi
72
28 (72%)
3
97 (70%) (61) CN
(CH,),CH,CN
1) LDA, O", THF. 2) oxidation
SPh
"h
w
(62)
CSPh
92%
benzylic tertiary amines was directed exclusively to either the 2 or 6 position of the aromatic ring, depending upon the substituent at C-3. Since these complexes can be functionalized at the palladium carbon bond, this procedure is of some synthetic interest C7391. Applications of a-ally1 transition metal complexes in organic synthesis has recently been reviewed (58 references) [140] as has organomercurials reagents and intemediates
in organic synthesis (235 references) Cl413.
as
219
Me$iCH$lgCl
0
+
NiC1y
r
Me$i&COOH
-Q95%
(0% without
v
Ni)
(63 OOH
-
LiN(SiMe?)?
Me3SiCH2
91%
ci R
&
R
I--
A
R
-
(64)
k
R = CN,
COOMe
+
R
0
0
R
4%
I
t
I
Ce(IV)
/
-
(65)
R’ 0
23
/
CN
1) 2)*
TCNE
CHO Fe(COj, (66)
Fe(CO)s References p. 303
220 Theses dealing with _in situ generation and use of tris(triphenylphosphine)Cl427 and a-carboalkoxyvinyl copper reagents Cl431 have recently
nickel
appeared. B.
Conjugate Addition
Organocuprates
continue to be the reagents of choice for conjugate of enones. Most current work centers on the development of new
alkylation reagents
and their
to the total synthesis of large molecules.
application
The new organocuprates
Li Cuz( Me) a, Li&u(Me)s and LiTCus( were studied While each show different, in their reactions with conjugated enones. solvent-dependent behavior, ii2Cua(Me)S in ether gave excellent results
with
all
enones
tested,
of added lithium studied.
and reacted
iodide
faster
or 12-crown-4
The crown ether
(2 equiv.)
than R,CuLi [144]_
on the reactions completely
MepCuLi wi th 4-methyl cycl ohexenone (con jugate (al kyl ation)
and the
Lithium iodide
enol acetate
lowered the yields
Me2CuLi, but did not completely conditions
for
reaction
in the synthesis conjugate
(eq.
67) [146].
the reaction
addition),
hexanoyl
acetoacetate
stop the reactions_
were without
of lithium
of R&uLi were
inhibited
any additive
Lithium methyl-,
(1-dimethyl aminoethyl )phenyl]cuprate
reagents
iminati
relative
to
The most efficient at al 1 [145].
acid and dehydroabietic
dimethylcuprate
of
chloride
(addi tion-el
of each of these reactions
of both podocarpic
addition
cyclohexenone
of ethyl
The effect
acid was the
to the appropriate butyl-
A key step tricyclic
and phenylC(+)-2-
were prepared
and reacted
wi tt
(67)
R’ methylcinnamate.
[147-J. thesis
transferring
R” the methyl,
butyl
or phenyl
groups
Divinyl cuprate additionstocyclopropylacrylicesterswas of (r)-eremophilone (eq. 68) Cl483. A new organocurpate
selectively usedinthes. containing
221
-+ *
l
0
(68)
0 eremophi
“Ox”“+ (MejC-CsC+-CU
lone
+
_
boEt
0SiMe3
bSiMe,
0
*
2.
(69)
Qr 0
References p. 303
222 a protected (eq.
acrolein It reacted
69).
steri c hindrance methylene
well with conjugated
in high yield addition
by free
radical
Prostaglandin
addition
(es.
70) Cl511. cyclic
jugated
The
axial,
while
Best results iodide
the menthyl
ester
addition
of phenyl,
copper
of alkyation
substrate
2.2% optical
catalyzed
Mixed cuprates
yield
yield
of
the
and
esters
cuprate
71) C1521.
with the intent
having
7.5% yield
of
cuprous
complex (eq.
was obtained
a 65% yield
Grignard
con-
stereospecifi-
has been reported.
and a mixed
and in the presence
cuprate,
of
osides
systems involving
with E-furanoacrylic
with 10% optical
mixed
but only Copper
studied.
the
of substrate
same chiral
tained
of
a variety
completely
using heterogeneous
at the site
went in high yield
produced complex mixtures.
group as the nontransferrablemoiety.
methyl ester the
occurred
than the tri-n-butylphosphine chirality
with
[150].
of a cyclopropyl
With hex-2-enopyrano-4-ul
alkylation
of organocuprates
of inducing phenethyl
organocuprates
hex-1-enopyran-3-uloses
were obtained
rather
The reaction
The reaction
by
enones,
olefin
using the alkylation
were studied.
hex-3-enopyranosid-2-uloses tally
of
as
while allylic
to conjugated
HBr to the tenninal
as a key step.
reactions
lactones
fell
w-Bromoketones were prepared
Fza was synthesized
ketone by a mixed cuprate
studied
an approach to C-
were unreactive
divinylcuprate of
reactions
but the yield
offered
halides
[149].
of lithium
and its
enones,
This chemistry
Vinyl and alkyl
lactones.
the conjugate
group was synthesized
increased .
halides-alkylated followed
alkyl
of
added
Using
a chiral
a
of conjugate [1537.
lithium
conjugate
addition
continued
to
With the chloride
and
was ob-
[154].
reactions type
also
[RCuMe3lgX,
be extensively
where R was allyl,
OSi-tGuMe, 1 R,SiO--
+
C3H7C=C-Cu &sH,,
OSi-tBuMep
(70)
/
HllCs
+ %
OSiR, 88%
+
*
PG F,r
223
4 -2
MeLi BuaPCuI
+
OEt
R = trityl (71) OR
Me LiMe?Cu
CHz=CH-CHzCHz-, transfer and
the
the
tion
containing
substrate
was
the
CHz=CH- (CHz)s-
and group
was
main
the
reacted
with
3-methylcyclohexenone,
(75%)
product
methylation
A variety
[155].
and organocuprates to Z-furanacrolein has t-butylmagnesium
salts,
high and
halides,
while
1,4
with
concentration LiMe2Cu
addition
to 1,4
addition
by running
the
benzyl from
(69%)
reactions
methyl
to transfer 40-50X
yield
Trisubstituted addition alkynes
with
the
alkyl
(alkyl
low
favored Copper
(68%)
than
and
ally1 allyla-
tetrasubstituted
and
were
substrates
copper(I)
were
group,
produced
and
bromide
or
was true.
addition.
Both
using
vinyl
A
MeMgI/CuI
conjugate
slow
(41%), "ate"
producing
n-butyl,
also
1,2
iodide,
i-butyl,
by the
to conjugated
catalyzed
isopropyl
reverse
catalyzed
Copper
stereospecifically
reagents,
the
and
(80%),
p reduced
With
addition
to good
yield
addition
of
In this fashion the following groups
[157].
(not methyl)
cuprates,
iodide
rather
was achieved in fair
temperature
n-pentyl
= n-propyl,
olefins
2,3-butadien-l-01
p. 303
(54%),
trialkylborates
by Grignard
copper(I)
References
at
cyclohexyl
of vinyl
Allenic The
Ph
and
R was
by using
favored
C156].
to suppress polymerization.
were introduced:
to primarily
when
of tri-
made.
halide
reagent
of Grignard reagents to ethylacrylate
acrylate
been
was
benzylmagnesium
of Grignard
led
enones
However,
ii comparison of 1,2 and 1,4 addi-tion of Grignards
enones were examined.
iodide
conjugated
unsaturation.
reactive
Shexenyl
reacted
with
synthesized catalyzed
enones
(eq.
towards
of alkyl-
trans
RCHzCH=CHCHzOH
prepared
ethylpropiolate
E alkylacrylates n-hexyl)
copper
reaction
(73L),
complexes,
72)
by conjugate alkylation
complexes.
phenylmagnesium [160].
of
[159].
organocopper and
in
C1581.
Conjugated
halides
: '
R3MgBr
f R’+
RlCH=CH-C-R2
H
Rb
RQ R3 = Et,
n-hex,
R4 = n-hex,
enone
=
-f
R1
R2
0
nBu
Et
p$Ph,
pf12
69
ms
+ (low
CH2=C=C
yield)
,COOEt ‘H
(73)
RIR’C=C=CHI 70%
OAc R3p_CuLi
-I-
R1R2kCSH
-+
H
R~R+C=C=C’
R1R2-C-CXH R3’
‘cu
‘R3
(i
I
I 0
&,
R4
45-60%
R’R2C-CXH ;HzOMe 75%
225 allenic
esters
underwent 1,4 alkylation
was reacted
with an allylic
73) Cl613.
Propargylic
allenic
cuprates,
(eq_ 74)[162]. enolate
halide,
acetates other
formed by conjugate
surprising
reacted
which were further Several
observation
cases
addition
that
alkylation of the enone (the less ted cyclopentanones were prepared. [163].
dialkylated
The conjugate
followed
by treatment
offurtherreaction
have been reported.
Based on the led to cis
stable product) several cis 2,3 dialkylaB-Vinyl groups did not have this effect,
of lithium
dimethylcuprate
Finally,
to produce
of the copper
addition
of the enolate
which (eq.
with a number of reagents
with vinyl
with two equivalents C165].
with organocuprates
treated
were obtained
3,3,5,5-tetramethylcyclohexanone addition
lavandulol
species
rea:snt) led to the production hexanone in good yield [164]. P-en-l-one
ultimately
!3-phenyl groups on cyclopentenones
a
and trans
to produce a copper enolate,
producing
cuprates
(eq.
75)
to cyclohexenone
with Me2N=CH‘CFsCOO- (a new Mannich
cycl oof B-methyl, a-dimethylaminomethyl Treatment of 3-chloro-5,5-dimethylcyclo-hexof lithium
dimethyl
in 76% yield
dimethylcyclohexane
cuprate
produced
by combined alkylation-conjugate dicarboxylates
were obtained This
by the addition of lithium dimethylcuprate to methyl crotonate.
1) Me7CuLi L 2 ) MeI
(75)
but 0
0 1) (0,CuLi 2) -or-
_-
(ia
less than 3% cis
69% // Me
0
COOMe
H;:
A
OMe
+
RR' CuLi
F;
(76)
ti dOOMe
49:: References
p. 303
product
arose
from a sequence
of
1,4
additions
and a final
cyclization
(eq.
76)[1667. A variety
of other
Treatment
of zinc
produced
a complex
in THF at O” for
have been used to effect conjugate additions.
metals
halide
with
[IRsZnLil
thirty
three
which
minutes
to copper.
These were then 77)
(eq.
Cl681.
1,4
alkylated
[167].
from al kynes by hydrozirconation
enones
equivalents
coupled
cyclohexanone
Vinyl copper
followed
Similar
of organolithium
to dienes
were prepared alkenyl
or added 1,4
was effected
CuCl
in 94% yield
species
by stereospecific
chemistry
reagent
transfer
to conjugated
by transfer
of the
l 3’ \ -
[\
cu
+CaC=H
90%
i-
-
(7
\
Cp,ZrHCl
Cp,ZrC
3)
Hz0
\
0 73%
RI
R2
I)
Cp?ZrHCl
R2CXR1
2) H
/ T
R4 3
Ni
(acac),
0
>
HsO’
(Zr) (71
R1 = t-Bu, R2 = H,
Me,
n-hex, Et
Et,
CsHI,CH201\Omonosubst. disubst.
Substrate
alkynes al kynes
50-95% yields 6-10% yields
227
vinyl
group to nickel
(eq.
78) [169].
The conjugate
addition
of
butyl-
magnesium bromide to (Z)-(ZR,3S)-6-benzylidine-3,4-dimethyl-5,7-dioxo-Zphenyl perhydro-1,4-oxazepi hydrolysis
99% enantiomerical Arylpailadium
complexes,
in a similar
promoted 6-arylation
prepared
chloride,
fol 1owed by
of 3-phenylheptanoic
by the ortho
enones to replace
The a-alkylpalladium
amine reacted
by nickel
gave a 92% yield
acid
ly pure [170].
added 1.4 to conjugated [171].
ne catalyzed
and decarboxylation
complexes fashion
of conjugated
(eq.
palladation
the palladium
resulting
of benzylamines
by the enone (es.
from methoxylation
80) 11727.
enones by aryl
Palladium(O) halides
(eq.
79)
of allyl-
catalysts 81) C1737.
Both E-bromo and 3-bromothiophene reacted with ally1 alcohols in the presence of palladium acetate catalysts to produce aldehydes or ketones in a formal s-alkylation
of ally1
alcchol
(eq.
82) Cl74,
1751.
\ K?
(79)
0
-
2
92%
+,
7
References
9
0
p_ 303
fai1s
,
Tph,
%
a or a alkylation
also
work
slows reaction
228
NMe,
Me0 Me + PdClz
+ MeOH
0 XS EtsN rfx PhH
+
+
Me2
(80)
(81) COOMe
67% COOH
JoH
7OH PhBr
+
f
OH
,
60-981
yield
0 also
work:
/
ToMe
t
Titanium to conjugated
an angular
BreCHO,
tetrachloride
ally1
reaction
carbene
anions
group
also
promoted
The
enones.
tetracarbonilferrates The
BraCN,
method
in a fused reacted
went
added
with
1,4
the
BraSMe,
conjugate
was used decalin
with
for
system
conjugated
acrylonitrile
to d,B-unsaturated
(eq.
addition
the
direct
(eq.
enones 84)
83)
ieq.
1,4-diketones.
Finally, 85)
of
Alkyl
[176].
to give
C1771.
compounds
of allylsilanes
introduction
[178].
chromium
229 R Br
Pd(OAc)? cat. HMPA 100%
+ 9 OH
.
+ dH
+H
0 40%
RX
+
yield
Na*Fe(CO)&
-+
5:4
R E(CO)L,
+
mixture
' Tf
R = n-Bu,
References
n-hex,
p. 303
Et
0
-
RC@T
0
230
/L
/ A
COOEt (92%),
m
COOEt (82%),
A
COO-t-Bu (83%),
I\/\/\/*
/
-COOEt
(84)
/ A
CN (95%),
(61%),
CN (92%)
-
\
1) base
(CO)&-
2) ’ ?f
-+
(CO),Cr
(85)
x
0
0 Cl %
Acylation Phase transfer C.
catalysis in carbonylations of organic halides has been to the corresdeveloped by two groups. Benzyl bromides were carbonylated ponding phenylacetic acids by reacting the halide, carbon monoxide and a catalytic amount of Coz(CO)s in a benzene-5E NaOHsystem, using triethylWith o-methyl benwl benzylammonium chloride as the phase transfer catalyst. bromide,
a double
in addition
carbon monoxide insertion
to the normal prcducts
chloride,
carbon monoxide,
[179].
occurred A similar
to give ArCH(COCOOH)CHzA system using benzyl
sodium tetracarbonylcobaltate
as catalyst,
with a
diphenyl ether-aqueous sodium hydroxide solvent system produced phenylacetic acids in 85% yield C180]. Iodobenzene was converted to methylbenzoate by treatment
with carbon monoxide in the presence
palladium
or nickel
Cl-is
alkyl
in alcohol
iodides
in methanol-diethylamine were converted
86) [183]. acyiiron
Allenes complexes
Cyclic and polycyclic
solvent
ClSl].
to the corresponding
with carbon monoxide at 200-250a
zeo? i te catalyst C1821. o-bis(bromoinethyl)benzene
of tetrakis(triphenylphosphine Straight
esters
in the presence
of a rhodium-NaX
2-Indanone was produced in 80% yieid with sodium tetracarbonyl cobaltate
were acylated
to produce u,B-unsaturated
via a n-heterobutadiene aliphatic
by treating in THF (eq. ketones with
iron complex (eq.
compounds were synthesized
chain
by treatment
87) [184].
by the insertion
231 of olefins ability Many
and
carbon
to chelate,
products
monoxide and
were
into
terminal
often
nickel-carbon
vinyl
obtained
groups
(eq.
88)
bonds.
were
[185].
Strained for
Grignard
reagents
with aryl halides and carbon monoxide in the presence
reacted nickel
dihalide
alcohols
complexes
Cl867.
of organic
halides
ences)
with
and
appeared
to produce
Reviews with
the
[187,
dealing carbon
mixtures
with
metal
olefins
monoxide,
carbonylation
of ketones
transition
of organic
olefins,
required
and
and
reaction.
of dialkyltertiary
catalyzed
reactions
acetylenes
halides
(44 refer-
(70 references)
have
1881.
NaCo(CO),,
+
x
(86) 80%
NazFe(CO)k
f
RX
f
-J
CH2=C=CH2
t<, \
R
30-60:; R = Et,
n-Pr,
n-Bu,
n-hexyl
(87) also 0
NaZFe(CO)I,
+
BrCH21 Y,CH=C=CH/
Dialkynylmerclry
compounds
reacted
at room temperaturr in the presence dialkylmaleates the
Cl :9].
treatment
nickel
(el.
stereochemistry
rhodium
catalysts
hydride
and
olefin
for both
the
production
maintained
aldehydes
References
C1927.
p. 303
was
complex,
palladium(I1)
arylmercuric
and
catalysts
diarylketones
hydroformylation
examined.
groups.
isomerization
of a rhodium
monoxide
were
halides
alcohols
to form
synthesized
in the
by
presence
of olefins was the subject of extensive
of the was
fonnyl
carbon
of
89)[190].
The hydroformjlation The
with
with
of
Unsymmetrical
of a .yliodides
carbonyl
/ ?Y
-f
The studied
Both
mechanism [191-j.
triphenylphosphite
of normal
catalyst During
the
course
and
of both A new
from
cis
the
system
acetate
a-olefins.
was
The
formation
reaction
cobalt
addition
and of
the
hydroformylation
catalyst
sodium
promoted
of this
with
promoted
and
aldehydes
activity
of olefins
metals
research.
and
consisting developed
sodium
acetate
of normal
traces
of oxygen
in
I
232
-Cl
+
CO f
Hz0
+
Ni cat.
-
(88)
Very reactive
W,
5+JE+
,
0
,
45 0
Unreactive
PmR
’ , 0,
0
,
0
R*I +RyJ-Hgx O Nio,
P-2 ’
,
l
\
(89)
R'
R
60-90X
R = H, 4-Me, 4-NH2 R' = H, 4-Me, 4-U
the synthesis catalyst.
gas oxidized
the phosphite
to (PhsO)sP=O, deactivating
the
toluene
Scrubbing of the synthesis gas with triisobutylaluminum in suppressed this oxidation 093-J. The hydroformylation of deuteratec
o?efins
with cobalt
catalysts
and the data obtained olefin
Ti-complex 0941.
at high carbon monoxide pressure
were consistent The percentage
with initial conversions
formation
was studied, of a catalyst-
in ethylene
hydroformy-
233
lation
over
Rit(C0)Cl[P(CsH~R)slz
frequencies
of
the
hydroformylation phosphine
correlated
phosphorous-rhodium
of
ethylene
adsorbed
over
on y alumina
step
c1961.
Cyclic
to give
dienes
depending
on ring
underwent
?arger
ring
compounds
lation
(eq.
9O)C1971.
hydrofonnylation ditions
the
moderate
of
1-pentene
clusters
rather
as a rate with
to
give
intact,
acetamono-
dialdehydes
were used
for terminal hydroformulation
the
propionalde-
than a second
and 500-1200 remain
of
favored
at
to
loss
a catalyst
rings
clusters
130°,
triphenyl-
bis
hydrofonnylation
carbonyl
were claimed
selectivity
Cl981.
reduction
of
carbonyl
with
as Small
vibrational
The kinetics
Rh(I)H(CO)(PPhs)z
underwent
size.
Cobalt
infrared
I)
were consistent
tocarbonylbis(triphenylphosphine)rhodium(I) dialdehydes,
the
T;-allylrhodium(
hyde from Rh(III)Hz(acyl)(CO)(PPh~)2 limiting
with
bond C1951.
to
psi. yields
and
while
hydroformycatalyze
the
Under these
con-
were high,
and
was observed (eq. 91)
The catalytic activity of rhodium(I) complexes as hydroformylation
/ -t 0
CO
\
+
Hz
+
cat.
Rh(I)
dH0 catalysts
depended
the
phosphines
led
to
of
state
of
both
phosphines
to
polymer
bound phosphine
or
at
two
most
of
Substitution
coordination. by one
phosphine
of
a fi
of or
one
of
trisphosphine
complexes of higher activity than the parent complex, while
bridged
substitution
on the
RhH(CO)z(PPhs)z
polymer
gave
ligands
bound
complexes
led
to
phosphine
of
trans
groups
lower
square are
Compl exati on
activity. planarcomplexes
coordinated
in
[199].
which
A
CHO /\/+
+
Hz
+
CO +
cat.
-+
wCHo
+
(91)
cat.
=
catalyst consisting
of
60-80”
psig
References
and 800-1500 p. 303
(PhsP)zPtClz-SnC12 Hz/CO to
give
hydroformylated 85-903
yields
of
e olefins aldehyde
at with
234 85-93’6 selectivity
for
was hydroformylated optically
active
of catalyst
straight
chain aldehydes
aldehyde
C2017.
The product
in the hydroformylationofethyl
methyl crotonate was studied.
Startinq
to phenyl or cyclohexyl
phosphine
[203].
using a palladium olefins
and related
hydroformylation
in high yield
stereospecificaily
With R equal
was observed,
while
tertiary
phosphines
and
in the rhodium carbonyl-tertiary
of 1,3
dienes
to dialdehydes
was asymmetrically catalyst C2041. were obtained carbonylation
under mild conditions
with (Ph3P)2Ni(Ph)Br
of Hz/CO
or RhzClz( CO), alone gave
has been reviewed
Linear a,s-unsaturated esters and (MesPPh)2PdC1z-SnC12 catalyzed proceeded
the catalyst_
80% a acylation
as cocatalysts
reactions
methyl methacrylate,
The use of aliphatic
a-Methylstyrene dichloride-(-)DIOP
as a function
diphosphines of various chain
triphenylphosphines
C2027.
phospholanes
catalyzed
vestigated
and n = 2-4,
distribution
acrylate,
with RhzC12(C0)4,
diphosphines,
very low a-selectivity P-substituted
a-Deuteriostyrene
at 150“ and 100 atmospheres
and methyl tiglate
length (R,P(CHz)n PRz) were added to generate
use of longer
[2007.
in the presence of a chiral rhodium catalyst to give
was in-
hydrocarboxylated Hydrocarboxylation
of
[205]. by the (ArzP)zPdClz-SnClz The reaction of 1-alkynes.
[I2061.
2-Butyne reacted
in methanol to give
a vinyl
complex
which upon carbonylation produced 98% a-a,&dimethylcinnamate c2071. Treatment of acetylene-hexacarbonyl dicobalt complexes with alkenes or cycloalkenes were obtained strates reviewed
for
produced cyclohexenones. (eq.
92) [208].
the synthesis
(258 references)
With unsymmetrical al kynes,
Carbon monoxide addition
of quinones,
acrylic
mixtures
to acetylenic
and succinic
acids
sub-
has been
[209].
(92)
30-60% R = H, Me R’ = H, Me, Ph
Several
new olefin
carbonylations
monoolefins were aminoacylated,
have been developed.
Simple terminal
by treatment with diethylamine followed by
carbon monoxide in the presence of palladium(I1) chloride, to produce 8aminoacid derivatives after oxidative cleavage (eq. 93) C210].
Transition
metal catalyzed carbonylation of olefins was reviewed (289 references) [211] Isoprene was acylated to produce 4-methyl-3-pentenoate
esters by treatment
235
with carbon monoxide in the presence catalyst
of a palladium
acetate-triphenylphosphine
system.
converted
Cyclic olefins -No isoprene dimers were formed f212]. to exocyclic trial kylsi lenol ethers by treatment with carbon
monoxide,
trialkylsilane
, and dicobalt
octacarbonyl
(eq.
R -
+
PdC12(CHzCN)z +
R2’NH +
CO
were
94) [213].
R2’
N
‘Pd’
* %
Cl ‘NHR2 ’
0
(93) 1) Et-?, -78O 2) BH 0
60-70% BH = CH,OH, NH,, EtzNH
+
n = 3
48%
n=4
71X
n = 5
74%
n=6
69% Oxetane,
CO +
COT(CO)*
THF and epoxycyclohexane
methyldiethylsilane carbonyl
HSiRs
to give
(94)
were cleaved
by treatment
and carbon monoxide in the presence
rrith
of dicobalt
octa-
Et2MeSiO(CH2),CH0 and Z-(methyldiethylsiloxy)cyclohexane
ether carboxaldehyde C2147. Vinyl silanes reacted with dichloromethylmethyl in the presence of titanium tetrachloride to produce conjugated aldehydes w-unsaturated alkylsilanes were acylated by in good yield (eq. 95) [215]. treatment
with titanium
Metal oxides
tetrachloride
the acylation
at 150”.
Anisole,
halobenzenes
using FezOa
in high yield
by substituted of a separate References
p. 303
(eq.
96) [216].
such as Fe203 ZnO, Moos, (NH4)sMo7,0zG~4H20 and Na2GI0,
catalyzed tion
and acid halides
of isomeric
xylenes
with
and alkylbenzenes C2171.
benzoic acid chlorides report C2187. Pyridine
benzoyl acylated
The benzoyl ation
chloride
in 10 hr
in the four
posi-
of ha1obenzenes
catalyzed by Fe2(S0,)s was the subject was treated with phenyllithium followed
236 Rl
R2 +
M H
Cl,CHOCH,
(95
SiMes
H
CHO 72-85'5
R1 = n-pentyl,
n-Bu,
Ph,
n-propyl
R1 = H, n-propyl
(961 0
RM
_,_
It
R&j
O-28%
by iron
pentacarbonyl
not
normally
The
Gatterman
trichloride
to give
accessible Koch and
38-63:;
direct
acylation
to electrophilic
reaction
Cu(PPhs)Cl.
of toluene
in the
substitution was
promoted
Triphenylphosp1,1ne
6 position, (eq.
97)
by mixtures
inhibited
this
a site
[219]. of aluminum reaction. CHO
Ph 73%
COOH C ii
(’ Ph
t?
-R
24-323
23'i OC1 -I-
ti
COCl
fe(CO), (98)
(CO)3Fe
(99)
m OtBu
/
1
+
f
Fe(CO),
(100) cage dimer 14%
References
p. 303
Bu,O
+
linear trimer ketone 78%
238 The iron tricarbonyl
complex of the acid chloride of cyclobutadiene
dicarboxylate acylated 4,4'-dimethylbiphenyl
(eq.
98) C2217.
bony1 and crotyl
The reaction chloride
c2221.
primarily
acylated
of endo dicyclopentadiene
in acetone-water
Iron pentacarbonyl
to give a polycyclic complex
reacted
dimers (eq.
with nickel
gave a tetracyclic
with 7-t-butoxynorbornene
100) C2231.
Norbornadiene
car-
acid
(eq.
99)
to give itself reacted
with iron pentacarbonyl and alkynes to give polycyclic ketones (eq. 101)
Lactones
t224J.
were formed by the photolysis of unsaturated epoxides in
the presence
ofironpentacarbonyl
from similar
treatment
Finally, cyclic
an unusual series olefin
iodide
developed
though maximumactivity of these metals. examined [2287.
(eq.
carbonylation
No significant
in detail.
promoted reaction
102) c2251.
ketones
resulted
103) [226-J.
and rearrangements
of iron
of methanol to acetic
acid was
was noted between the methyl
by rhodium or iridium
was achieved
under different
Iridium was the best catalyst Ketone solvents
(eq.
104) C2271.
difference
catalyzed
Cyclic
cyclopropanes
of carbonyl&tions
complexes was reported
The recently studied
(eq.
of unsaturated
complexes,
conditions
of all
such as acetophenone
for
aleach
the platinum metals and benzophenone
600Me(COOEt)(Ph)
(101) +
HCK-COOR
-
COOR 15%
kept both the activity elevated conditions
temperatures involving
was found to also effectively
and selectivity C2291.
of this
In a departure
methyl iodide
as a promotor,
promote the carbonylation
than methyl iodide
12307.
ated compounds has been reviewed
reaction
high,
from the standard
reaction
pentachlorobenzene
of methanol,
The carbonylation
(103 references)
even at
L-2311.
although
thiol less
of saturated
oxygen
Arnines were car-
239
0
d/
m 0
(102)
\
70%
O
\ Qr 0
(103) (no yield
bonylatec! carbonyl
to formamides by treatment via iron
a-diketones and an alkyl
with carbon monoxide and iron penta-
carbamoyl complexes
by sequential iodide
(eq.
treatment 105) [233].
[232].
and mechanistic
aspects
Acetals
were converted
with butyllithium. Transition
for organic synthesis has been reviewed
thetic
given)
metal carbonyl s as reagents
(81 references)
of inorganic
insertion
C2341, as has synreactions
Reviews on carbonylation
reactions
C2361, and the chemistry
of potassium tetracarbonylhydridoferrate
references)
References
under mild conditions
C235-J.
(53 references) (17
(I2371 have appeared.
Decarbonylation the topic
to
iron pentacarbonyl
of a thesis
p. 303
of racemic aldehydes C2381.
with chiral
Decarbonylation
reactions
rhodium complexes using transition
was
240
(104)
0
43 R = Ph, Et, n-Pr, Me R' = Me, Et
metal compounds has been reviewed
(144
references)
C2391.
The stoichiometril
decarbonylation of (S)-(+)-PhCHDCOCl with tris(triphenylphosphine)rhodium(I) gave (S)-(+)-PhCHDCl in 20-27X scrambling labelled also
between chloride.
examined.
substrate,
overall product
stereospecificity. and catalyst
The decarbonylation The results
favor
Rapid
was detected
halogen by using
of C6DsCD2CH2COC1 to styrene was
a mechanism
in which
a rapid
preequili-
brium between acyl and al4ylrhodium complexes is followed by a concerted cis
24 elimination
of
rhodium
hydride
[240-j.
Substituted
(styracins) containing hydroxy substituents
cinnamyl
in the aromatic rings decarboxy-
late8 .cO 1,5- ~~a~~-l,Pf-p~rrtacti~rres crpun tredtmenc pal 1 adium catalysts 0.
cinnamates
with
platinum
and
L2417.
Oligomerization
The cationic complex produced by treatment of bis(triphenylphosphine)pentachlorophenyl(chloro)nickel(II)
with silver perchlorate catalyzed the
dimerization of ethylene in bromobenzene amount of
added
dimerized
by Ziegler-type
palladium(I1) in the for
triphenylphosphine
the
of
aluminum halides
of
of
effects
isomerization
the
arsine
propylene
phosphine
highest
based
ligands [243].
activity
of
chloride
selectivity
for
the
Catalytic
nature
complex
having
the
of
highest
alkyl-
the
ligands
catalyst,
2-methyl-2-pentene
systems
halides,
or stilbene
the
ligand.
strongly
with
triphenyl-
isomerization
[244].
activity
Brominated
polystyrene was treated with (tetrakis)triphenylphosphinenickel(O) resin bound nickel( II) boron
trifluoride
efficient
aryl complexes.
etherate
catalyst
solvent
although
C245;.
Zerovalent
for the
the
nickel
dimerization
of
amount of
water
propene.
N-hexane
was completely
complexes
such
insoluble
and [(ptoly-O)sPJzNi(CHzCHz)
or trifluoroacetic
acid,
produced
best
solvent
[(EtO)3PlnNi,
when treated
catalysts
an
was the
in this
as (PhaP)kYi,
(Ph,P)zNi(CHzCHz),
were effective
to form
Treatment of these resins with
and a catalytic
catalyst
was
and
and alkylaluminums
on n-allylnickel to
Propylene
nickel(I1)
base
by arsine
A catalytic
C2421.
planar
ligands
were sensitive
ligands
and diethylaluminum
and the
Schiffs
containing
and ligands
Replacement
activity
from square
chelating
phosphorus
dimerization
enhanced
catalysts
complexes,
presence
at O” and 1 atm.
for
with
olefin
sulfuric
dimerization.
The catalytically active species was thought to be a nickel hydride C2461. Polynuclear palladium(I1) complexes were implicated as the active catalysts in the
oxidative
was involved tive
dimerization
of styrene
in the rate limiting step 12471.
dimerization
of
for a-methylstyrene,
olefins
in the
presence
C2501.
2500 was produced
of
was completely was studied cyclooctadiene The starting ally1
saturated of
by treating nickel, material
isomerization
Referencesp. 303
by treatment
pentacarbonyl
The mechanism
the
oxida-
were studied
C248, 2493.
Polycyclohexane
cyclohexene
and ethylaluminum and the
rings
the nickel(O)
with
triphenylphosphine rapidly
isomerized through
molecular
dichloride.
were retained
catalyzed
of
a catalyst
u-complexes
from
The polymer of
1,3-butadiene with
in benzene to the
weight
prepared
C2517.
dimerization
cis,cis-1,4-dideuterio-1,3-butadiene
proceeding
of
palladium(I1)
and isomerization polymerization of unsaturated
hydrocarbons has been reviewed chlororhenium
The kinetics of
stryene and l,l-diphenylethylene
Hydrodehydropolymerization
Pdj(Ohc),
to 1,4_diphenylbutadiene.
bis-
at room temperature.
trans,trans 12527.
diene Mixtures
via
an
of
di-
242 methyloctatriene isoprene
isomers were formed by the tail
over phosphine pailadium(0)
CO2 assisted
to tail
complexes
dimerization
in the presence
of
of CO2.
The
in the formation of the catalytically active species c2537.
The selective
dimerization
by catalysts
prepared
metal halides
of butadiene
to 4-vinylcyclohexene
by the metathetical
reaction
was effected
of NaFe(C013NO ivith
such as CM(NO)aXlz where M was Fe and Co, and X was Cl,
Br
and I C2541. A proper amount of water was found to enhance the catalytic activity of sodium borohydride-amine-bisphosphine nickel dihalide catalyst systemsforthe
dienes
with n-propylamine,
attacked
The principle
dimerizationofisoprene.
monoolefins
and cyclic
ones with pyridine
such as styrene,
propene,
Me2C=NMeat the carbon atom of highest coefficient nickel
in the lowest
catalysts
C2561.
reactions catalyzed references) [257]. prepared selective
long life
cyclooctadiene. lifetime. catalyze
unoccupied
Oligomerizations,
A nickel catalyst
for
The catalyst
It catalyzed reduction
of olefins
value for
electron
density
polymerizations
and other
complexes havebeen
of
diolefi?
reviewed
(20
complex Ni,(CN-t-Bu)7,
and t-butylisonitrile
was an excelleni
of butadiene
cyclotrimerized of alkynes
and
in the presence
the dimerization
also
reduction
Butadiene
[2551.
orbital,
cluster-isonitrile nickel
were linear
methyl methacrylate
absolute
molecular
by homogeneous nickel
from biscyclooctadiene
products
to cis
alkynes. alkenes,
to 1,5-
but had a short but did not
12581.
The combined oligomerization-nucleophilic
M
+
attack
sequence
involving
CHsCOOH Pd(OAc);?, PPhS 1
1 //,
OAc I
OAC P,z,
OH-
RuC17_L3
i OH
I
Pd(OAcj2,
&
PPh3
(1061
1 j i-BuzAlA 2) LiAlHJ Cp2Ti Cl 4
OAc H70+
&
243 butadiene
has
presence
106)
of
to prepare
reacted
a variety
with
triphenylphosphine
Butadiene
c2591.
presence
used
Butadiene
compounds. the
been
reacted
acetic to
with
of
acid
give
unsaturated
a-ether
esters
and
u-hydroxy
107)
polyolefinic acetate
in
act-1-en-3-01
acids and
(eq.
palladium
ultimately
of bis(acetylacetonate)palladium(II)
produce
interesting
or esters
(eq.
in the
triphenylphosphine
C2601.
The
queen
bee
to sub-
R M
+
Pd(acac)? 2oo, PPhs
HO-iH-COOR'
’
(107)
A/\
COOR
R = H, Me R' = n-Bu,
Et
/-,
COOEt
Pd(OAc)_, PPhs
•I- CH,(COOEt)z
COOEt
95x
PdCl?
CuCl,
l
+COOEt
H?
02 COOEt
67%
+cooEt
(108) COOEt
COOEt 47%
References
p. 303
dil.
KOH ;Lw
\ queen
bee
substance
COOH
244
-
+
CH3N02
Pd(OAc);, PPh,
l
/
/ /
--++gy-+ NO2
87%
(109) OH
Ho-OL/O 86%
rii -L
1) Cr?O,, acetone 21 Na, xylene
L
-
60%
92% cis
civetone
stance
was synthesfzed
in
presence
the
of
palladium
t.2613.
cis
Civetone
acetate
(eq.
109)
carbon
monoxide
by the
reaction acetate
was prepared
C2621,
while
and t-butanol
triphenylphosphine
(eq.
/w,
f
butadiene
and diethyl
and triphenylphosphine from
royal in
110)
of
the
nitromethane,
jelly
acid
presence
(eq.
butadiene
was prepared of
pal ladi
malonate 108) and palladium from
um acetate
butadiene, and
C2631.
CO
+
Pd(OAc), PPh3
t-BuOH
CO2(CO)R
/e
MeOH
COOtBu 90%
(110) COOtBu
/
MeO,CW 62%
hydrolys
i s
\
HOOCn./\/\/\/C
OOH
80%
royal
Ni(acac)
00
+
,/
+
COD
f
+
jelly
AlEt,
CF,COOH
acid
+
(Ar0)3P
+
catalyst
;“;;1,‘& (Ill)
t 64%
33% 62%
Use of
Bu,P
+
984
m
n Nwo
References
p_ 303
-P!
246 Reduced morpholine butene
nickel
species
to give
mixtures
or octadiene
butadiene amines
and
(eq.
trisubstituted
(eq.
Ill)
palladium
piperdines
reaction
from
to give
+
and
RaP
+
amines
octadienyl
system
urotropine
with
reacted
with
substituted
produced
EtaAl
with
at nitrogen
Primary
catalyst
butadiene
?-'(acac)
of butadiene
substituted
[264].
species
A similar
[265].
the
of morpholines
groups
reduced
112)
cata?yrsd
1,2,3-
(eq.
113)
[266].
Catalyst
+
NHCH2Ph f
-i- e
PhCH2NHz
CFqCOOH
catalyst
~
-
-JW
(112) +
I/\
+
‘-
(-
+
NHPh
[Pd(acac)
)2NCH2Ph
-AraP-EtsAll
+
urotropin -f
(113)
Hydrazones
react
at nitrogen
with
in the presence of a
butadiene
palladium(O) catalyst, while related nickel catalysts cause reaction at the hydrazone carbon (eq. 114) mixed
oligomerization
presence The
of morpholine
polymerization
C267,
268].
The
product
of N-benzylidenepropylamine was
and
dependent
distribution with
on morpholine
copolymerization
of
of the
butadiene
concentration
butadiene
has
been
in the [269].
reviewed
C2701. Metal a very
catalyzed
useful
paration
cyclotrimerization
approach
of benzocyclobutanes,
cyclooligomerization (eq.
115)
chemistry
to polycyclic
C271]. was
used
indanes
of a,w-diynes An
absolutely
to synthesize
of alkynes materials. and
with
elegant the
has The
tetralines
substituted intramolecular
steroid
skeleton
been
full via
developed
paper cobalt
acetylenes version (eq.
116)
into
on precatalyze\: has
appeared
of this C2721.
247 Transition been
metal
reviewed
catalyzed
acetylene
cyclizations
in organic
synthesis
has
C2733.
2
MeNH
L,Pd
'N
'm+
l
RI
R2
/ W-N
I Me
86%
<
R’
R’ = H, Me (114)
~2 = Me, Et
‘-
+
MeNH,
R’ N
(CoD!7Ni
+
-R’ Rl Rl
N=NMe
t
60:40
mixture
=-RI Z-R -
2
f
40-60X
Ill I
R"
cpco(co)q
+ (R3 or R4 must
be -SiMe3)
(115)
n = 3-5 R's
= SiMe,,
References
p- 303
COOMe,
H, Ph,
hexyl
Me2SiCrCSiMel CpCo(CO),
(116)
estra-1,3,5(10)-trien-17-one
Ynamines underwent cycjotrimerization 1,3,4_triaminobenzenes of
nickel
of
3-hexyne
bromide
(eq.
bromide with
117) [274].
A catalyst
mesitylmagnesium
to hexaethylbenzene
complex
[2757.
using a nickel bromide
or
dimerized
complex which, ketone
upon oxidation
(eq.
by treatment
to
nickel (E)-(3S,7S)-3,7-
1,3,5-tris[(S)-1-methylpropyllbenzene
tetrachloride, depending on
condi ii ons . No racemization was observed [276]. dimerized upon treatment with palladium chloride gave a cyclic
to give
cyclotrimerization
via a tetraethylcyclobutadienyl
when treated with triisobutylaluminum-titanium
palladium
prepared
catalyzed
(S)-3-Methyl-1-pentyne
dimethyl-4-methylenenon-5-ene
catalyst
Phenylmesitylacetylene to give
a stable
vinyl-
with chromium trioxide-pyridine,
718) C277].
R
LsNi(C0)7, CH&N,
R-IX-NR2’
50”)
(117)
3 hr R NR2 ’
R = H,
30-50x
Me
Diynes cyclized rhodium(I) cycle
with alkynes
in the presence
to form complex polycyclic
‘(rhodiocyclopentadiene)
eq.
materials 119
[278]
of tris(triphenylphosphine via an intermediate
and eq. 120 [279].
metalla-
Chromium
carbene complexes of the type (CO)sCr=CPhR reacted with alkynes to give
chromi urn coordinated the coordination
s-naphthol s .
The naphthol
sphere of the metal (eq.
skeleton
121) [280].
was assembled in
249
PhH 48 hr, 25” ’
PdClz(PhCN)z
(1181 Ph CrOq-Py CHzClz ’ 24 hr
Ph
Aesityl 46%
R rPh I
L,RhCl i
+
R’CsCRz
--Ph
R G
0
Ph
R = H, Me, Et
The effect rhodium(I) product
I.
complexes
ligands
was studied
distributions.
phosphine i281
of phosphine
and the total
on the dimerizationofl-alkynes
in an attempt to alter
linear-to-branched
No simple correlation
between steric
yields
of the reaction
Treatment of terminal
or selectivity
by
bulk of the was discerned
alkynes with triisobutylaluminum
and nickel,
iron or manganese salts led to alkylation-dimerization (eq. 122) [282]. Cyclotrimerizationof isoprene with hexafluoro-2-butyneusing n5-indenylrhodium(bisethylene)
complex as a catalyst
1,2,3,4-tetrakis(trifluoromethyl)-l,3-hexadiene reacted
with alkynes
chloride
to give
cyclopropane References
p.
303
in the presence
codimers
gave ns-indenylrhodium
of palladium
chloride
which are 1-halo-1,3-butadienes
ring opened and oligomerized
when treated
Sisopropyl-
C2831. Styrene and lithium [284].
Vinyl-
with phosphine
250
ZPh
+
L?RhCl
R'C=CRl
~
=Ph
(120)
OH ,Th
+
(CO)sCr=C
R'CrCR'
+
(121)
'I? Cr(CO),
R 7-68X
R = Ph,
OMe
R1 = Et.
Me,
R2 = H, Me,
nickel(O) depended Propene with
Pr, Et,
Ph COOEt
complexes on the was
phosphine
to yield
phcsphine
converted
butyllithium
pol_ymerized
ether
Bu, Ph,
to
and
cuprous
polymerized
dihalide
chloride
and
in 50% yield
a nickel(O)
of products,
the
123)
1,2,2-Trimethylcyclo-
[285].
[286].
by treatment
catalysts
the
reacted
catalyst
with
magnesium
same
conditions ally1
to give
catalysis
and
oligomsrization
has
been
reviewed
by transition
of ethyl [289-J.
acrylate,
metal
by treatment was
metal
and his-
[287].
chloride,
a compound
with
(eq.
complexes
acrylonitrile
of which
4,4'-Dibromodiphenyl
with
rings with high selectivity and stereoselectivity Nuc7eophilic
composit'ion
Q-Dibromobenzene
in 90% yield.
under
trans-1,5,9,13_Tetradecatetraene monoxide
(eq.
2,3,6,7-tetramethyloct-4-yne-2,6-diene
to poly Q-phenyl nickel
a mixture
present
three
124)
cyclopentanone
[2881.
including and
trans, carbon
dimerization
crotononitrile
251 R Ni(MeSal)T
~ \
R-
30-66%
RCECH
+
(i-Bu)sAl
~
FeCl?
l
(122) 65%
Mn(acac)x
l
IBu-i 78%
/
(123)
90% yield
Cl
+
Ni(0)
of mixture
-+
(!24)
References
P. 303
252
E.
Rearrangements
The
olefin
symposium
in September,
been pub1 ished chloride
and metal and
yield
case
by suppressing
of
selectivity
ethanol
l-pentene,
butyltin
and
was
in the
Crafts
reactions
used
(1:4) The
was
and cocatalysts
tri ethyl al uminum [I2947.
subjected
such
hexachloride-tetrabutyltin of
linear
and
as the
tungsten
alkenes
by adding
hexa-
disproportionation
polymerization
of
hexachloride-tetra-
S-6-methyl-P-octene. 1-Pentene
using
not
tetraethyltin
system
were
The
did
tungsten
were metathesized
catalyst
chiral
solvent
the
to metathesis
esters
2-heptene.
from tungsten
as tetrabutyltin,
w-Olefinic
triethyl
with
benzene
catalyzed
as well
C2921.
now
hexa-
hexachloride-tetrabutylti
prepared
to disproportionate
Methyloleate
tetrachloride
A variety
with
have
tungsten
reactions
tungsten
A catalyst
symposium
from
(+)-(3S,lOS)-3,10-dimethyl-6-dodecene.
C2937.
tungsten
achieved
international
diethyltin,
in their
and Z-P-octene,
was
of this
as tetrabutyltin,
aluminum hydride
of an
prepared
studied
Z-cyclononene
catalyst
product
proceedings catalysts
C2917.
2-pentene
topic
such
Friedel
and lithium
the
were was
or esters
Z-cyclooctene
react
alkyls
was
The
Metathesis
butyllithium
High
chloride
1977.
[290].
alumfnum
ether,
reaction
metathesis
(eq.
subjected
or
using
the
125)[295].
to the
metathesis
(125) 83-93%
n = 2,
6,
n=8
X = CH,OAc
reaction
of
X = COOMe
8
with
chiral
this
activity
and
trans-4-octene such
by addition catalysts Pyridine
of
the
in the
isobutylaiuminum
1297-J.
of oxygen
pentacarbcnyl
aluminum dichloride complexes
CZ991.
catalysts
were carbene
and
homogeneous
isopropylaluminum
promoted reactions
of
upon
(l,&cyclooctadiene)tungsten
internal
activation
of
of cyclic
and
propagated
trans-3-hexene
R = Me', Ph)
dichloride
metathesis
by the
upon
gave
and
olefins oiefins
union
via
com-
activation
highly
olefins
by treatment
terminal acyclic
the
c2961.
or tungsten-germanium
Sn;
linear
of
and that
on the P-alkene
produced
tungsten-tin
metathesis
Metathesis
C3007.
presence
the metathesis
configuration,
depended
(M = Ge,
molybdenum
chain
of
dichloride
Bimetallic
showed that
resu!ts
retention
catalyst
as vC.~H~W(CO)~-MR~
for
The
with
of trans-3-heptene
tetracarbonyl
a metal
catalyst.
occurred
and selectivity
Hetathesis
plexes
same
2-alkenes
active
C2981. with
methyl
metal
carbene
by molybdenum
of an olefin
with
253 Fulvalene diene)(bis c3017.
was metathesized
with ethylene
titanium)dihydride The conductance
trichloride
as L catalyst
of the solution
to a solution
using (fulvalene)(dicyclopentato produce ethane and butadiene
resulting
of W(CO)sClz(AsPhs)z
from aclding aluminum
in dichloromethane
was much
greater than expected, and was attributed to the formation of the catalytically active species C3021.
Olefin metathesis of cis-2-pentene by zero
talent tungsten catalysts both in the homogeneous phase or supported
inorganic
on
oxides were compared. With both systems the primary function of The catalyst
the cocatalyst was to decrease electron density on tungsten.
on a solid
support
fatty
acids
nally
unsaturated
had a steric
and esters
effect
u,w-diesters
to ethylene
[303].
as a heterogeneous
by a catalyst
prepared
w-Unsaturated
and long chain inter-
using rhenium heptoxide
small amount of tetramethyltin were metathesized
on the reaction
were metathesized
on alumina plus a
catalyst
by photolysis
13041.
Al kynes
of molybdenum hexa-
The reaction was thought to carbonyl in the presence of chlorophenol. occur by a two-step mechanism involving activation of molybdenum hexacarbonyl
by the alkyne.
and subsequent
of the phenol and the transition the two-stage
mechanism [305].
by Ph2CU(CO)s was highly actions
catalysis
by the phenol.
metal separately The metathesis
on silica
of cis-Z-pentene
, probably
stereoselective
Heterogenation
gel supported initiated
because of steric
in the four-membered ring transition state c3061.
inter-
The stereo-
chemistry of the metathesis of cis-2-pentene by zero valent tungsten catalysts showed that four different metallocarbene internal
were involved,
olefins
initiation.
types of coordination
and all
which are nearly
Stereoselectivity
had about the same rate.
symmetrical,
of cis
reaction
has been reviewed
several
times [308]
and tertiary amines in the presence transition
metal complexes
Several
new olefin
to use synthetical
olefins
For dominate the
was explained
(91 references),
disproportionated
of triphenylphosphine
on the
[309], to primary
and a variety
of
of Rh, Ru, Ir or Ni [311].
isomerization Catalytic
ly .
factors
to the
coordinated to tungsten and/or the C3071. The olefin metathesis
Secondary alkyamines
(60 references).
steric
and trans
basis of the steric bulk of the ligands configuration of the metallocyclobutanes [310]
of olefin
catalysts
isomerization
have been developed and put
of 1-pentene
to e-
and
trans-2-pentene by HzRu~+(Co)~s and HRus(CO)sCsHs cluster compounds in toluene involves metal hydride addition-elimination sequences and o-alkylintermediates, also
observed
although C3121.
endocycl i c double
some suggestion
of n-ally1
type intermediates
was
Normally difficult or impossible exocyclic to
bond rearrangements
were promoted by rhodi urn trichl ori de
However, treatment of ergosterol under these conditions gave tri hydrate. a complex mixture (eq. 126)[313]'. Cycloalkenones having exocyclic double bonds underwent isomerization
References p. 303
and disproportionation
to aromatic
Systems
254
when treated with chlorocarbonylbis(triphenylphosphine)iridium [3747.
(eq. 172)
The reagent generated from bi-cyclopentadienyltitanium
dichloride
and
R
and
lithium
giving
an
Allylbenzene
/ i!l-
l
aluminum
hydride
isolable
(1261
titanium
both
R
isomerized
and
was
rearranged
to trans-6-methylstyrene
carbonyl.
Usfng
deuterated
substrates,
out,
results
while
mechanism and
were
o Olefins
C317].
Co(olefin)PPhs
sulfonamides The
product
used
in situ --
presence
H
consistent
[318].
by treatment was
formed
in good
when
was
ruled
with
were
but was
Co(N2)(PPh3)s
rearranged
with
to N-vinyl-
irradiation.
difficult
to purify
and
was
Ally1 alcohols were isomerized to aldehydes in the
C3191.
of tris(triphenylphosphine)rhodium
0
treated
pentacarbonyl
yield,
shift
a 1,2-addition-elimination
N-allylsulfonamides iron
1-octene
C315, 3167.
by hydridocobalt
a [1,3]sigmatropic
with
isomerized
with
hydrometallated
Cp,Ti(A1H,)(C,H,,CH=CH2)
complex
carbonyl
H
hydride
in
OH RCH2
R
R
L,Ir(CO)Cl 250", 1 hr *
90% and
Ph
(127)
255 trifluoroacetic
of chiral
With a chiral
acid.
aldehyde were obtained
molybdates
o.
to carbonyl
C3201.
.*henates catalyzed
(eq.
present
alcohols
The vanadate
yields
low optical
Vanadate esters,
the isomerization
compounds and a-ethylenic
number of cases were studied. efficient
diphosphine
tungstates,
of a-acetylenic
to allylic
esters
alcohols
alcohols.
A large
were particularly
128) [321].
+
160” 30 min.
NaH,VOs
76%
(128)
Unsymmetrical and ketones
via
by Claisen 1-4
rearrangement
Diallylesters
treated
with
C3231.
A variety
allylvinyl
the is
presence
Fe(I1)
1,5-hydride
substitution dienoic
complexes
solvent
(eq.
and ring cleavage
with
in 59-90X
132)
(eq.
131)
cyclohexadienes 1,2-Arene
C326-J.
when treated
little
in the
with of
of
(eq.
with [Rh(CO),Cl]2
730) to the
chl orotri
s-
expected
intra-
decomposition
Substituted
or cyclopentadienes
oxides
129)
when
a-pellandrene
the
similar
[325-J.
(eq.
rearranged
by treatment
with
for
acids
ligands
oxides
Epidioxides
observed
epoxide
to
phosphine
stilbene
followed
(PhsP)sRuClz
and 8,y-w
decomposition
epidioxide
of
by olefin
abstraction
rearranged
0.19
retarded
at 159-210°[325].
promoted
acid
oxides
of
aldehydes
ethers
to a,6-w
benzyl phenyl ketones
underwent
on the
B,y-unsaturated
to
or rhodium
molecular levopimaric
to
of 4,4’-disubstituted
triarylphosphinerhodium
arene
rearranged rearrangement
rearranged
nickel
corresponding
with
The reaction
hr at 200°.
[322].
diallylethers
regiospecific
of
1.4depending
underwent deoxygenation [327].
dl-Muscone
was
synthesized by the ferric chloride cleavage of a 1,2(bis)(trimethylsiloxyl)cyclopropane followed by al kylation of the thus formed enol acetate by lithium dimethylcuprate The photoassisted in the presence is
a 1:l
a-complex
via the population References
of
p. 303
(eq. 133) [32E1]. valence isomerizationofnorboradiene
copper(I)
salts
suggested
that
the
to auadricyclene photoactive
of diene and copper and that photoreaction of
an olefin
metal
charge
transfer
state
species
originates of
the
complex
256 CHO TO_ 0.1X
200” ~ L3RUC12
1 S& 99%
and
O-
(1291
u I
+
CHO
97%
(130)
‘---?rH + -OH
0
66-73% mixtures
The quantum
[329].
complexes single to
give
yields
CPPh3CulBH,
bonds
underwent
rearranged
bicyclo[l enantiomeric
.l.O]butane excess
of
this
reaction
were
and CMePPh2CulBH4 C3301. rearrangement
hydrocarbons
best
upon treatment
compl exed to
iron
with
Strained with
the ring iron
(eq _ 134)
derivatives
were
kinetically
by treatment
with
a rhodium(I)(DIOP)complex
resolved
copper carbon-carbon pentacarbonyl Racemi c
[331]. in
up to which
30%
257
OOMe
CRh(CO)7Cl-J? CHCl,
COOMe
(132)
[Rh(CO)>ClJT MeOH
l
Et7Zn CHzIz
88”-
H7, Pd/C
/ G?c
d,l
muscone
co
I
hv
References
p. 303
(134)
.,omerized
selectivel,
one enantiomer
leaving
the other
merized
and ring opened to 1,3-
enantiomer
CRh(C0)2C172 C3333. [4.4.2]Propellanes hexacarbonyl
intact
occur,
and 1,4-dienes
rearranged
at 125” to initially
released rearranged material
to a substituted butadiene, while Vinylcyclopropanes were epic332l. by treatment
upon treatment form a complex,
(eq. 135) C334l.
with
with molybdenum which then upon heating
For the rearrangement
to
1,3-cyclohexadiene had to be laterally fused to a strained fourChromium hexacarbonyl and tungsten hexacarbc;,yl form
membered ring _ stable
complexes
kinetics
of this
of benzene, (eq.
reaction
normally
135) C3367.
methyl shift,
which do not rearrange.
Deuterium isotope
effects
and
have been examined [335J. A Diels-Alder dimer was stabilized by coordination to iron
unstable,
Camphene rearranged
in the presence
to isobornyl
of copper(I1)
chloride
acetate
without
C3371.
>125O
l
CD I
-
a
(135)
i
Fe(CO)s
Ce(IV)
l
(136)
259 III.
Oxidation Electrophilic
of cyclohexene
epoxidation
as a heterogeneous this
system
plexes
was
as rle$COOH,
than
similar
as
of the
30-50%
yield
molybdenum 138)
excess
ligands
(eq.
and
lo-30%
complex
with
epoxidation
compounds
state
to that
PhCHMeOOH
enantiomeric
acids
(eq.
the
were epoxidized
alcohols 50%
similar
by PhMe2COOH
were
catalyzed
The reactivity
catalyst.
catalyzed
such
oxidation
of propylene
by t-butylhydroperoxide
peracetic
of ally1
and
alcohol
was
using
vanadium
[340].
optical
purity
olefins
by organic
or titanium,
and
unimportant
with nerol
by PhCMe200H
chiral were
and
more the
C3391.
in high yield and
towards com-
hydroperoxides much
catalysts
Geraniol
epoxidation
Vanadium
was
by t-butylhydroperoxide 137)
of
13381.
Vanadium
tungsten
.!um compound
the
by Mo205(Me2NCS2)2
a variety acid
PhCMe2COOH.
of mr'ybdenum, van
of
and
active initial
Allylic
and up to hydroxamic
epoxidized
the
in
chiral
(acetylacetonatoX(-)-N-alkylephedrineldioxomolybdenum
L-3411.
By carrying
+
t-BuOOH
out molybdenum
+
VO(acac),
and
vanadium
catalyzed
0
+
H
,AMe
Mev-*/'1, Me
*
“C~NR~H ke
R = Me, Ph, 2,6-xylyl
[
p&h
gave
best
optical
yield
(l”)
OH +
PhCMezOOH +
-+
R7B1/-o” (138 R’
References
p. 303
epoxidation
of
that
hydroperoxide
intact
olefins
by hydroperoxides
in H,‘aO,
was present
in the
epoxidation of olefins by hydroperoxides
it
active
was demonstrated complex
The
C342J.
using molybdenum(V)
complexes
with ligands such as ethylene glycol, lactic acid and amygdalic acid in homogeneous
systems,
as well
as heterogenized
catalysts
exchange reactions of Na2[Mo204(0X!2(H20)~.3H20 Oxovanadium(IV) resin
was studied C3437.
compounds were incorporated on a sulfonic acid ion
and used as catalyst
for
the
reaction
than did
comparable
indicated
that
homogeneous
the mechanism
epoxidation
of
the
exchange
of t-butylhydroperoxide
This epoxidation was much more selective
olefins.
by ion‘
prepared
with
and went in higher
reactions.
heterogeneous
Kinetic
reaction
yields
studies
was similar
to
The same vanadium compounds were incor-
that of the homogeneous case C3441.
porated into several insoluble polymers containing ligand groups such as acetylacetonate,
ethylendiamine
the epoxidation of
the
of
sodium molybdate
peroxide
was zero
was considered mixtures
to
and No(O,),(OH)~ thought
to
L2Pt02
+
in moderate
-7130
RCOCl
6 and substituent
by osmium tetroxide conformation
of
selectivity rin9
of
were
the the
reactant
A conformation
(Table
The stereochemistry process
effects
was the and that
reacted epoxidized
references) oxidation tions)
[350].
for
ethylene
[351]. of
equilibration
factor
of
that
the
determining
substituents
the hydroxypalladation
Studies oxidation
on the
A4-steroic
ring
the
merely
step
A
stereo-
anchored
the
in mechanisms
in acetic
2- and 1-acetoxyethylpalladium(I1)
threo-1,2-
trans-1,2-
of
new homogeneous
was found solution
solutions.
of
of
have been
in aqueous acid
in the Nacker
formation
development
to acetaldehyde
by palladium(I1)
same reaction between
(139)
1) [349]. of
A difference
ethylene
and the
c348].
hydroxylation
was shown to be -trans by the stereospecific from the Nacker reaction
Catalysts
nor-
l
dideuterio-2-chloroethanol dideuterioethane
with
I
0
in the
primary other
of molybdenum was
which 139)
epoxidatic
Mo(Oz)(Cl),(OH)2
chlorides
It was concluded
investigated.
reaction
(eq.
1
‘O-O-C-R
Stereochemical
Acid
yields
acid,
complex
complex
/Cl
l
The epoxidation
In molydenum catalyzed
[347].
peroxyacid
The kinetics by hydrogen
peroxide.
and hydrochloric
agent
to catalyze
[3451.
allylalcohol
The monoperoxide
epoxidizing
LaPto
of
hydrogen
[346].
peroxide
an intermediate
and cyclohexene
to
in nature
were present.
bornene
epoxidation
respect
hydrogen
be the
to give
with
be polar
containing
by &-butylhydroperoxide
catalyzed
order
and were used
and pyridine,
cyclohexene
reviewed
in the
(Nacker In acetic prior
(56
catalytic condiacid,
an
to decomposi-
261
Table
1
Hydroxylation
Olefin
of A"-Steroids
4~~,5a diol,
A4 3a-OAc,
A’
A'
3a-OAc,
19-Nor,
A4
36-OAc,
19-Nor,
AL
Pa-OAc,
A4
2~-OAc,
A’
tion
vinyl
to
2
98
87
13
11
89
77
23
62
38
8
92
was proposed,
while
CO formation-hydride
shift
3,3-dimethyl-1-butene,
gated
cyclooctene,
copper(I1) mechanism using
[3533.
chloride of the
palladium
aromatic
sequences
by palladium
in detail
The
reaction
unclear
complexes,
i-
PdCl,
+
CuCl,
acid
several 140)
the
concerted
oxidation
of cyclo-
cis-2-hexene
solution
%
C3547.
making
Organic
by
was investi-
by palladium
products,
oxidation
(187
conditions
and
of norbornadiene
(eq.
including
The
l-hexene
gives
been reviewed
has
[352].
in acetic
oxidation acid
under blacker
occur
acetate
in acetic
compounds
diol,
>99
acetate
catalyzed
4s,58 76
hexene, oxygen
%
24 A4
38-OAc, 19-Nor,
by 0~0~
chloridethe
synthesis
reactionsofolefins
references)
and
[355].
m
+ OAc
(140)
x
d&L
Y!YzLoAc+ Aco The
oxidation
chlorohydrins
and
of olefins vicinal
examined_
The
containing
chromium-carbon
oxidation
of
reagent
of olefins
with
aryl
nickel(I1)
chloride
pinene
References
by manganese acetate p. 303
and
involved bonds
such
chromate-iodine
en-3-01
dichlorides
mechanism
olefins
by chromyl
as
or alkyl
triacetate
a cis
c356].
a-Iodoketones
141)
produced acetate,
addition
styrene
6-Oxyselenides
(eq.
to produce
epoxides,
process
of organometallic
selenocyanates
in methanol
myrtenol
via
formation
1-hexene,
C357l.
chloride
OAC
produced
by the
and
cyclohexene
were
produced
by the
in the
presence
of copper
C3581.
a-terpineol as well
were
was
intermediates
The
oxidation
acetate,
as other
by a silver
of
reaction
a-pin-3-
materials
or
(+)--CL-
c3591.
262
Oxidation of (+)-3-carene by manganese triacetate gave nine products C3603.
The application
organic
compounds
0
of manganese
triacetate
has been reviewed
as an oxidizing
(61 references)
reagent
_,.SePh
+
I
PhSeCN a
0,
ROH
OR’
100%
and
(141)
PhSeCN CuC12/MeOH +
RCH,=CH
RCH-CH2
,
OMe
-I- RCH-CH2 !iePh
;ePh
I-Octene
was catalytically
a&oxidized
tris(triphenylphosphine)rhodium Tri phenyl phosphine C3621.
chloride
was necessary,
The same rhodium
Triphenylphosphine
porphyrin hexene
catalyzed
oxide
the
complex
There
with
2-octanone oxygen
oxidized
by treatment
at 1 atm and 25O. to
triphenylphosphine
was used to catalyze the oxidation
and phenols inhibited the reaction C3631.
conversion
with
hydroperoxide in essentially quantitative of
and cyclohex-1-en-3-ul,
acetylacetonate.
to
and this
of cyclohexene to P-cyclohexen-l-y1 yield.
&ie
clO%
>87%
oxide
for
c3617.
cyclohexene by oxygen
were 5 x lo3
moles
of
to a 1:l
mixture
and molybdenum product
formed
Iron(III
of
cyclo-
or vanadium per mole of
iron porphyrin C3641. Terminal
alkenes
were oxidized
to
primary
alcohols
by hydroalumination
by lithium aluminum hydride catalyzed by dicyclopentadienyltitanium followed by oxidation of the thus-formed alane.
yields, while terminal olefins gave fair to excellent yields. both
terminal
position
and internal
[365].
Moos-HYPA (eq. nones (eq.
Dihydropyran 142)
by treatment 143)
olefins
[366]. with
reacted
selectively
was oxidatively Vinyl
oxygen
ring
cycl obutanes
at the opened
Dienes having terminal
by treatment
wore oxidized
and palladium(I1)
dichloride
Internal olefins gave poor
to
with
cycl openta-
chlsride/copper(II)
chloride
c3671.
(142)
Primary ch-ioride,
alcohols
oxygen
were oxidized
and an amine.
Benzylic
tnd allyiic
aliphatic
alcohols.
alcohols Secondary
to aldehydes
The best reacted alcohols
by treatment
with
copper(I)
amine was 9,10-phenanthroline.
faster gave
and gave
better
ketones,
but slowly.
yields
than Benzyl
263 amine was oxidized
to benzonitrile
PdCl?/CuClp Oz/HzO PhH, 25O
R
Secondary
oxygen
alcohols
smoothly
provided
were
and
compared
to that
aldehydes
nonaqueous
(eq. and
144)
C3717.
ketones
by
CsF5). C372].
Jones
reagent
air
complex
75% 82%
R =
65X
CH2NHCOMe
salts
unsaturated
for
and
was
While
used
for
kept
in solution
oxidation
of ethanol
the
and a small was
OS;
catalyzed
of
of alcohols
reagent
were
was
reagent
in eq.
oxidized
R = CFs,
C2Fs,
osmium
catalyst
the
145.
to facilitate
piece
all gel
chloride
Collins
alcohols
than
oxidation
2-
a,8-unsaturated
(M = Ru, reactive
was
oxidation
by Collins
secondary
more
the
in methylene
gave
with
be!lzyl alcohol
on alumina/silica
alcohols
chlorochromate
were
citrate
(143)
E-Propanol,
and
proceeded
(PhsP)2M(CO)(02CR)
trisodium
C3687.
by treatment
catalyst.
adsorbed agent
reaction
Primary
catalyst
yield
in high
acetate
chloride
pyridinium
ruthenium
chromium(II1)
of
conditions
R=H
cyclopentanol
oxidizing
The
these
R = CN
usingpyridiniumchlorochromate.
The
The
Chromyl
ketones.
epoxyaldehydes.
aldehydes
to ketones
chloride-sodium
The oxidation
at 25°C370].
of
oxidized
f-3691.
under
R
cyclobutanol.
a neutral,
to aldehydes
tion
4
cyclohexanol,
reacted
gave
'
and a palladium
octanol,
in 90% yield
The
produced
isolation
amalgamated
to
by addi-
mossy zinc
[373].
by a cobalt-o-diaminoazobenzene
[374].
Collins reagent CHO 69%
but
(744)
pyridinium chlorochromate
h H
.* x
CHO
98%
Benzaldehyde chlorobenzene oxidized
was
at 25O
to carbon
of carboxylic Referencesp. 303
acids
oxidized via
to perbenzoic
a radica,l mechanism
dioxide,
and
by treatment
ketones with
were oxygen
acid
by
c3757.
(PhsP)zPdOz Carbon
oxidatively and
cleaved
Rh6(C0)16,
in
monoxide
was
to mixtures
(PhsP)aPt
or
264
Jones reagent
(145)
80%
IrC1(CO)(PPhs)2 peroxide
at elevated
oxidized
temperatures
1,3-dicarbonyl
and pressures
C3761.
compounds in the presence
Hydrogen
of tungsten(V1)
or molybdenum(V1) compcunds [377I]. Chromium trioxide oxidized at the allylic position [3787. alkaloid c3791.
was oxidized Taurocholanic
solution [380-J.
1,4-cyclohexadiene and tri-t-butylcyclopropE The benzylic position of an isoquinoline
by VOFs to give
a 61% yield
acid was autoxidized
to methyl-l&-hydroxy-%-cholan-24-oate Iron(I1)
oxidation
(eq.
induced decomposition 147) C381].
of +-cataline
by ferrous
146)
and methyl lithocholate
of a rigid
The catalytic
(eq.
ions in aqueous
epidioxide
oxidation
led to remote
of paraffins
dMe
such
6Me 61% + cataline
as isobutane
or propane on ternary
C382, 3831.
Naphthalein
salts
to give
products
was selectively copper(I1)
oxidized
reacted
of radical
oxidation
to anthraquinone
bromide in ethylene
Substituted
NiO-A120s-Si02
catalysts
with oxygen in the presence
glycol
(eq.
148j [I384].
was studied of iron(I1) Anthracene
by oxygen in the presence
solution
of
[3857.
e-carbol ines were aromatized by treatment with Rh(PPhs)eCl.
Rh(PPh,j,(CO)Cl or Ir(Ph3P),(CO)C1 (eq. 149) C386, 3871. Isoxazoles were prepared from the dihydro compounds by treatment with Y-manganese dioxide (eq.
150) C3881.
carboxylation
Palladium on carbon effected
via a s-allylpalladium
an aromatization
complex (eq.
151) [389].
with deBoth piperidi
and cyclohexanone were aromatized by palladium chloride or tetrachloroSpi rocycl opentanenaphthalei ns palladate(I1) ion in aqueous base c3903.
265
9”
r
& Me
FeSO,
/* 0
* Me
/‘x Me
COOMe
CHMez ‘. .* 0
+
**
COOMe
28%
(147)
0 0 03
•I-
[email protected]+
Fe(II),
0,
0 (148) a-naphthol +
HO
aromatized
with
contained
rearrangement
in polycyclic
bromide/lithium with
dehydrogenated
t-butanol
.
phosphine
References
stereochemistry
with
with p_ 303
group with
rhodium
potassium
(eq.
153)
palladium
cases were studied
PhsP(CHz)sPPhz
by treatment treatment
junction
carbonyl
(eq.
Cycl ohexanones
with
Aromatization and without
[392-J.
154)
[393].
copper(I1) occurred
a halogenation
Ketosteroids
were acid
The chelating
in
di-
to Ph2PCH2CH2CH=CHCH2CHZPPhZ
or i ridi urn cyclooctadiene C394].
C31113.
chloride-hydrochloric
was dehydeogenated cyanide
152)
by treatment
acetonitrile.
by treatment
Nine
(eq.
in refluxing
of ring
nonconjugated
pal ladium
systems were aromatized
bromide
conservation
of the
over
B-naphthol
complexes
followed
by
H
3 3
i?RhCl
/\-
(149) N R’
R
R = H, Me R’
=
PhCHe, Pr
y-MnO:,
R1 = Ph, n-octyl R’ = H, NO2
(150)
, Me, s-naphth,
COOMe
,,,COOMe
R3 = Me, Ph,
Cobalt(II1) hydrazones, the ly
in fair
coupled
benzylcyanides
methylene
c3987.
cleaving
ketone
C3951.
40% yield
in 35% yield, with
and oximes
N,N-Dialkylanilines by treatment
copper(I)
tosyl-
with
palladium(I1)
C3963.
Benzyl
and 6-phenethylamines chloride
to
were oxidative-
to
and oxygen in
The mechanism of the catalytic oxidation of triphenyl-
to triphenylphosphine
was reported
at
group came from an acetate
to benzonitrile
in about
pyridine C3971.
efficient
2,4-dinitrophenylhydrazones
to high yield
to 4,4’-diaminodiphenylmethanes The extra
amine was oxidized
phosphine
was very
dimethyl hydrazones,
ketone
acetate.
trifiuoride
Aromatic
oxide diazonium
by oxygen and a Pt(Oz)(PPhs)z salts
were converted
catalyst
to the corres-
267
0
OH
CuBr7, LiBr CH$N rfx '
R
R
b
0 85%
-
(153)
o&
_ Ho* 75%
0
ponding phenols in high yield
by treatment
with
CA,0
and
CU(NO~)~
in water.
This procedure was superior in all respects to the acidic water procedure C3991.
Aryl Grignards were oxidized to phenols by treatment with
Referencesp. 303
268
0
t-I&OH PdCl z/HCl ’ 80°, 20 hr
(154)
Hexahydrocolupulone
Moos-Py-HMPA in THF at -78”[4001.
was oxidized
in
cyclohexane and small amounts of alcohols in the presence of copper(I1)
acetate
to give
cyclopentenediones
(eq.
155) [401].
ROH CU(OAC)~ '
(155)
R = CHMez,
RO-
IV.
Reduction There was a great
deal of activity
in the area of catalytic reductions,
with much emphasis on asymmetric reductions and solid phase supported catalysts
The complex from biscyclooctadienerhodium(1) methylphenylcyclohexylphosphine catalyzed in 46-982 yield of pyrrolidine
and 13-67% optical carbamate esters
yield
chloride dimer and chiral the reduction of conjugated acids Chiral diphosphines (eq. 156) 14021.
(I-III) were used as ligands
the reduction of N-benzyloxycarbonylaniline
on rhodium for
in 50-60% optical yield C4031.
Using a long chain ester group on these ligands gave a hexane soluble
catalyst
which reduced the ketone group of c ketoesters
in 99% yield
with
67.3% optical yield [404-J. Structural requirements of the chiral diphosphine ligand in rhodium asymmetric hydrogenation catalysts were carefully studied C405, 4061.
The response
of enantiomeric
excess
in the reduction
of CH,C(NHCOMe)COOH and PhCH=C(NHCOMe)COOH using rhodium(I) complexes of a series of diphosphine ligands was examined. The differences in enantiomeric excess
was claimed
(Table 2).
to be related
to the structural
rigidity
of the ligand
Changing the substrate from the acid to a series of esters, and
alteration of the aromatic group had little effect on enantiomeric excess t4071.
The rhodium complex with the (S,S)bisdiphenylphosphine
prepared
from
269
+
[Rh(COD)C7]2
*
catalyst
(156) R' R'
OH
/
+
+
catalyst
+
Hz
H
R
+
0
0 yield
ee
46%
13.5%
98
67
atropic E-B-methylcinnamic a-methylcinnamic
70
61
a-acetocinnamic
80
44
53
52
itaconic
rx
Ph,P
Ph2
?h2P
N
CH2PPh2
k
;O-t-B"
COCH,
;OO-t-B"
(SS)PPPM
(SS)APPM
(SS)BPPM
III
II
I
H,PPh*
‘cx, N
CH,PPh,
0PPh2 [(diolefin)RhCl]2 d
f ligand
+
=‘OPPh2 IV
Table
2.
Effect
of Chiral
Diphos
on ee
in Reduction
of RCH=C(NAc)COOH
DIOP
R=H
73%
72%
72%
40%
R = Ph
82%
86%
63%
35%
References
p. 303
catalyst
270
(R,R)-P,3-butanediol 92-100% optical catalyst
yield.
C4081.
catalyst
catalyzed
diphosphonite
(Diop gave 24% optical
phenylalanine acids
was observed
the molecular selective complexes
to (R)-Z-phenylbutane
yield
with this
yield
in
with this
yield.)
while
N-acetyl-
Unsaturated
carboxyli
while moderate stereo-
esters
asymmetry induced by olefins
in 60% optical
substrate,
low stereoselectivity,
with unsaturated
C409J.
The importance
of
in the enhancement of enantio-
dehydrogenation of racemic alcohols by (+)neomenthyldiphenylphosph or rhodium or ruthenium was investigated [410]. Asymmetric hydro-
genation
of cx acylaminoacrylic
catalysts
was studied
two carbonyl
groups)
in great
substrates
reduced
in only 1% ee (eq.
reduced
were much less
over
yield
acids
using chiral
biphosphine
“Tridentate”
detail.
gave the best optical
dentate
optical
in 83% optical
acids
IV formed a rhodium hydrogenation
was reduced in only 43% optical
were reduced with quite
selectivity
of N-acetylamino
L-Dopa was prepared
The chiral
that reduced a ethylstyrene
yield.
were
the reduction
V based rhodiu
substrates
yields
(olefin
(89-96% ee) whi!e
and
bi-
a Methylcinnamic acid a-Aminoacrylic acids and esters
stereoselective.
157) [411].
(S)-RhC1[PhaPN(CHPhMe)CH2CH2N(CHPhMe)PPh2]in49-843
II41 22.
+ gCODRhC1]2
NaBF,
+
catalyst
(157) CN
,COOH , CH,=C ‘NHCOCH$l NHCOPh
I ’ ,(h
Pd;;;;R
Me
A -
r(
NHCOMe
Ph
The use of chiral
ferrocenylphosphine
effective
for
hydrosilation C413,
4147.
(4-7%)
optical
chiral
bidentate
was derived carboxylic
asymmetric
reduction
of ketones
and for
Atropic yields
using
phosphines
the
C4157.
ligands
.
asymnetric usual
acid,
Grignard acids
rhodium
type
r( Ph
on transition
of a-acetamidoacrylic
of the
Prochiral
COOH
, 9% ee
and a-acetamidoacrylic
from (+)-camphoric acid
NHCOMe
-
, 51% ee
Ph
reduced in 89-96’i ee
) 1%
metals acids,
cross
was
for
coupling
cationic
catalysts
(-)-nopinylamine esters
asymmetri reactions
in low
were hydrogenated
Ph2PN(R)-CH2CH2N(R)PPh2
unsaturated
-
containing where
R
and (-)-pinane-3were
reduced
in up
271 to 76% 158) the
optical
E4167,
yield
while
corresponding
using
catalysts
bisphosphine
VIII
acids
ee
OPPh2
in 54%
f
derived based
(eq.
from
bisphosphite
catalysts
159)
C4171.
[(olefin)2RhC1]2
+
VI
were
used
The
complex
(eq.
to reduced L,Rh(amine)Cl
catalyst
0PPh2
(158) COOMe
ii
)_( -
+
100%
catalyst
H2
conversion
76%
optical
yield
NHAc
Ph
VII Ph
NHCOMe
H f
)_( H
H2
-
RhL"
(S)-PhCH&COOH iHCOMe
COOH
54” m ee ./here the
amine
amidocinnamic were
acid
obtained
phosphinite catalyst
was
in 80% yield
in the derived
was
corresponding
the
Rus
[421].
References
Ru4
p. 303
The
optical
system,
were
as
Reduction
used
acid. while
silica yields but
of the
catalyst,
ee [418].
reduction
High
catalyst
Up to 58% 61%
the
type
gel were
rate
with
and
was
ten
precursors
asymmetric
of a-acetamidoacrylic
used
comparable
induction
induction esters
was
using
(77:A)
insoluble
A Rh-OIOP
to reduce to those
times
for
yields
an
C4191.
H,Ruk(CO)sC(-)DIOPJ,
syrnnetric
of a-acetam-
optical
of P-phenyl-1-butene
compounds
(Z)-a-methylcinnamic with
20%
the
6-o-triphenylmethylcellulose
homogeneous
Ru~(CO)~~[(-)DIOP]~
catalyzed
to macroporous
acid.
cluster
and
hydrogenation from
attached
acetamidoacrylic
Ruthenium
d a-phenethylamine
slower
CLof the [420].
and the
reduction
was
of
observed,
obtained ruthenium
with catalysts
272 of the very
type
low
(~22)
resembling c4233.
RuClzLz
where
optical
DIOP
Benzil
yields
(VIII was
L was
and
iXj
reduced
the
chiral
sulfoxide
of reduced
product
led
ee
to 25%
to benzoin
EtCHMeCH2SOMe
in 79X
Using
C4221.
in the
reduction
ee using
containing
a ligand
genation
catalyst
C4251.
The reduction
The
of
change
The was
by rhodium hydride
ethylene and
black
benzene
over
to the
polystyrene
tri chl oride.
and
a cobalt
group
chirality
recognizing
(PhsP)sRhCl
supported
was
for
of this
glass
was
This
beads
The
system
transition
treated
polymer
polymer
[428].
counterpart
the
reduction
C4291.
chloromethylated,
reactivity hexene
of
with
which
changed in the
studied
catalyzed
the
support
Aging
under
benzene
hydrogen
led
ports
chloride polymer
measuring maximum
this (eq.
to the
[430].
reduction
dienes of Ti,
of synthesizing polymer 160)
attached
curve
extent
catalysts
rates was
Hf,
relative
observed
Nb,
such
to
porosity
were
The
reduction
loading
Ta,
for MO
and
for
W into
interactions
hydr of
polymer
sup-
and
and
hydrog
among
was probed by
loading.
Rhodium(I)
the
anion,
dichloride,
as Cp2TiC12
polymer
for
polymeric
introduction
cyclopentadiene metal
cycle
active
with
active the
of
and porosity.
particles
complex
of metal-metal
[433].
the
of
A method
polymer-bound
-The
C4321.
Zr,
homogeneous
was reacted
rhodium(I1)
bis-cyclopentadienyl
metallocene
hydrogenation in this
with
for
of metallic
[431].
of cyclocatalyst,
[(olefin)2RhCl&.
Rhodium trichloride
and
complexes
with
catalysts
formation
its
in their
to be a function
a paramagnetic
of monoolefins
consisted
treating
treated
boro-
effective
as was
differing
supported
and was found
hydrogenation
cyclopentadienyl
and
different
PhzPCHzPPhz producing genation
resins
[427
followed
sodium
metallocarborane
olefins,
at 68".
acid,
with
of
in the
abruptly
polymer
treated
supported
of hindered
phosphinated
was examined
bet
have
on a copolymer
was
o-aminobenzoic
was then
first
Polystyrene
these
hydro-
determined
function
~3,3-(Ph~P)~-3-H-4-(polystyrylmethylj-3,1,2-RhC~B~H~~l,wasan catalyst
catal.
monooxime
asymmetric
diphenyl-p-styrylphosphine
activity
ascribed
to give
hexene
of 2,3-butandione
of
a bis-dimethylglyoximato
catalytic
Chloromethylated
cobalt
ac
[426].
divinylbenzene
gas phase.
condensation
The structure
containing
(93 references)
styrene,
by the
[424].
complex catalysts with
Metal
reviewed
itaconic
IX
formed
1,3-propanediame
sulfoxides
of
a chiral
VIII
with
gave
The
catalysts
expected imnobilized
373 on phosphinate
styrene/2-20%
divinylbenzene
f 2
copolymers
were efficient
for
-i-
0
0
_3HCl
CpzMClz
(160)
G
/Cl
8
&Cl 0
the
hydrogenation
concentration
of olefins,
diolefins
and the role
and alkynes.
of uncoordinated
The effect
of substrate
phosphine was examined [434].
Transition metal complexes supported on phosphine modified silica gel carriers were two to four times more active as hydrogenation catalysts than the corresponding homogeneous systems. LaRhHzCl
,
LsRhCl
LzCoC12,
3,
tetrachloropalladate in the presence the reduction -4361.
L$liC12,
of ally1
alcohol
hydrogenation supported ethylene
than were their
on the polyion
and cyclic
dienes
system consisting phase,
in an immiscible
the solubility were obtained Treatment of
sodium
al kenes
of the olefin with this of
hydride
and
al kynes
catalyst
in
and propane the hydro-
olefin
phosphine
ladder
with rhodium(I)
[438]. for
for
tol!ards Colloidal
acid
olefin palladium
and poly-
the reduction
of linear
An unusual
was to use a two-phase
and product
Ph,P(o-SC3Na-Ph)
alkane as the organic complex of rhodium
aqueous phase.
The reactions were governed by in the aqueous phase. Very high conversions
system c4401.
10 equivalents
of
iron(II1)
THF and A-butanol (including
Ketones reduced only slowly, References p. 303
selective
homogeneous catalysts
and the water soluble
trichloride
and treated
were much more active
homogeneous analogs
of the substrate
a catalyst
were used for
to monoenes at 30” under hydrogen [4391.
approach to heterogenizing
LsRhHClz, Potassium
to produce
complex composed of polyacrylic
imine was the highly
,
coated with an organosilicon
phosphinated catalysts
L2NiBr2[4357.
propionaldehyde
on zeolites
Silica
LsRhCl
were
BaS04 or alumina and reaJced
hydroxides
to n-propanol,
C4371.
These supported
.
L2PdCl 2 and
supported
polymer was chloromethylated,
studied
on carbon,
of tetraalkylammonium
of cyclopropane
complexes
complexes
was supported
Platinum catalysts
genation
The
produced
phenylacetylene)
and olefins
could
chloride a black to
with
60
powder
al kanes
be reduced
equivalents which
reduced
quantitatively.
in the presence
274
of ketones. olefin
Vinyl cycJohexene
in 98% yield
hydride
in the
a black
catalyst
dienes
Treatment
[r4411.
same proportions which
also
A similar
by titanium hydride
or zirconium
Reduction
hydride
by dicycJopentadienyJpaJJadium
of the
reducing
reduction
cf
cataJyst the
reduction
hydrogenation
shorter
Rh(PPhs)sCJ duction
were compared with
Each reduced
3,7-dimethyloctanol. Palladium specific conditions
With
while
with
2tn carbon reduction (eq.
the
the
161)
[450].
K region
aluminum
olefin
[4441.
catalyzed
stereospecificity and BzHs in the
whi7e
on carbon
the rhodium
C4467.
were very
active
The catalysts
irreversibly
deactivated
J-Octene
was hydrogenated
by
to citrone77ol
one it
catalyst
The hydrogenation
the
first,
rethen
to
was considered
high yield
aromatics
and
in their
was simultaneous
for
of polynuclear
this
and
where L
Ru(PPhs)sClz
and rhodium metal
geraniol
over
PhP(CHzCHzPPhz)z
was the HaCoL species
homogeneous catalysts
was an efficient of the
studied,
The complexes
heterogeneous
was catalyzed
hydride
Palladium
triphosphines
catalyst
ruthenium
of the
on substituents
c447].
c4481.
in
dienes,
hindered
RhHzCJ(PPhs)z
olefins
of cheiating
phosphine
hydride
aluminum
was made.
but were
The most active chain
catalyzed
gave CHs(CH2)4CH(OH)CH=CH2
depending
dimers
least
A comparison
six
and
was
lithium
and CIr(COD)Lpy]+PFs
bridged
of geraniol.
sequentia7,
trans,
complexes
PhPt(CHa)aPPhz&.
all
alkanes,
resulting
nonconjugated
with
sodium produced
dichloride
With
on carbon,
of olefins,
of hydrido
and rhodium
was the
with
to
aluminum
added tc the
14457.
palladium
CIr(COD)L21+PFs-
formation
titanium
the exocycl i c
with
by HA7(NRz)z,
homologous to a-pinene
gave from 40-95%
compiexes
cobalt
systems
alkynes
lithium
dichloride
reduction
olefins
gave >90% trans
for
with
tetrachloride.
aluminum
selective
and
of reactivity
of CH,=CH(CH2)sCH(OH)CH=CHz
in a highly
of t-amylalcohol
and alkynes
hydroalumination
and lithium
acetate
presence
alkenes
The order
at
of nickel(I1)
Dicyclopentadiene
of alkenes
upon hydrolysis.
c443l.
excl usi ve reduction
in the
reduced
to monoenes C4427.
the hydroalumination reduction
underwent
[449]. regio-
under mild
of a-methylstyrene
by HMn(CO),
275
97% proceeded metal
by a free
hydride
pressure
to
using
radical
the
the
cluster
Coq(CO) 11 was inactive. of
reactions
for
path
substrate
involving
[4517.
catalysts Addition
the active
hydrogenated
to e-Z-butene
over
nickel
hexahydrate
sodium
chloride
borohydride
unsaturated cycl ohexene
The catalysts
.
selectively
reduced
efficient
were very
to monoenes
sensitive
cyclooctadiene was reduced to cyclooctene cycl ododecatriene decadienoate c4551.
to trans-cycl
to ethyl
ododecene
complex
and long-lived
duced
to cyclohexanes (eq.
162)
Conjugated [459], [460,
under mild
was highly
4611,
chloride
and with
reduction this
conditions
of
catalyst [457].
using
and all
2-acetyl -4,9seiectively as a catalyst was an efficient arenes.
Extensive
system Arenes
isomers
from both
were re-
[MesCpRhCl],
cis
fashion
100% selectivity
IrCl(CO)_(PPha),
reactions
were reduced
the
acid
IrCl(CO)L,
at 80-120”
(L = various
homogeneous
was prepared
hydrobromic
using
solvent
IrC1(CO)L2
for
conditions
with
the
with
were
In this
as a catalyst.
were the major
[458].
esters
catalyst
under mild
for
stereoselective
IrC1(CO)(PPhs)2without
efficient
with
of
to
trans-1,5,9-
n6-CsMesRu-n4-CsMes
was noted
and H2 + perdeuteroarene
The reaction products
catalyst
exchange
&,trans -3 and ethyl
with
reduction
Polyenes
to cyclohexenes
using
ruthenium,
homogeneous
hydrogen-deuterium 02 + arene
of
reaction
the
catalysts_
(93%)
was reduced
homogeneous
[456l.Aa-arene
(87X)
2-acetyl-4-decenoate
Neat 1,3-cyclohexadiene
in a photoinduced
(891),
[453].
exclusively
[454].
RuCl,(PPhs),
rates
hexahydrate
for
was reduced
air
over
chloride
catalysts
1,3-Cyclohexadiene
the
was selectively
complexes
or cobalt
low
while
enhances
1,3-Butadiene
cobalt(I)-bipyridyl
in OMF produced
compounds.
phosphites
[452]_
from the under
and CosRh(CO),,,
trimethyl
catalyst
atom transfer
was hydrogenated
Co,Rh,(CO)l, of
Treatment
of
hydrogen
Styrene
phosphines)
reduction
by treatment
and water
and photoactivation
and 10 atm of of of
hydrogen
[462].
A very
unsaturated H,PtCls
in alcohol
esters
and stannous
solvent
The
[463].
cationic rhodium complex CRh2(diphos)212f was an efficient homogeneous catalyst acids, transfer catalyst.
for etc.
the
reduction
[464].
hydrogenation The olefin
Molybdenum hexacarbonyl
References p. 303
of
Conjugated process reduced
simple ketones using
alkenes,
acrylic
were reduced
and amidoacrylic by P-propanol
via
a
RhCl (PPhs) s and RuCl2( PPhs) s as
first,
followed
in refluxing
aqueous
by the diglyme
carbonyl
C4651.
reduced
a variety
of
H2
+
15-%&l 15 eq. Et,N/catalyst Z-propanol
arene
+
'
hydrocarbon
(162) PhCOCH,
e.g.,
-f
PhNMe,
but,
Low
-+
PhEt
cobalt
(97%)
and
triisopropylphosphite n3-ally1
catalysts
for
saturated
ketones
composition
copper(I)
carbonyl bromide
with
acyclic
Sulfonated
soluble
reduction
of
catalyst
ketones
decanal
were
and
made
esters.
Both
HaCoLa.
ketones hydrides
and of
reduction
by treatment
complex")
"Li complex"
(14661.
selective
conjugate
"Na complex"
nitriles
and
was
used
of the
and
type
of
of
or
was
gave
best
for
highest
complexes
carbonyl
esters as
hRu(AcO)Ls
were
ligands
the
yields
reduced
and
groups
were
dependent
inert
ynones
(eq.
to make
RuClzLz
in aqueous solution.
oxoacids
IrH3(PPhs)s
which
were
with
reduced
hydrogen.
reduced
not
acetic
aldehydes
Conjugated reduced
to the
10 atmospheres
of hydrogen
compounds
not
were
type
were
Copper
were
yield
upon
the
water
for
The
163)
the
rates
of
pH of the
c4697. of
of
and
of the
the
("Li
The
triphenylphosphine
olefin
system
atmospheres
for
complexes
the
while
cataiysts
solution
Treatment
while
ketones
of unsaturated
reaction
(75%),
< 5% reduction
in high
hydrogen,
[467].
LiAlH(OCHs)s
, while
PhNO,
of a,&unsaturated
efficient
The
PhX,
ketones
amides
complex").
reduction,
i468?.
aqueous
COOMe
Aidehydes, ketones and halides were reduced at rates com-
parable to enone
reduction
("Na
unsaturated
in poor yield.
reduction
very
either
cycl ohexenones
of
PhOH.
L3 with
and
compounds.
NaA1H(OCHzCHzOCH,-)2 reduction
the
were
with
-+
complexes
cobalt
hydrogenation
conllrgated
PhC:CH,
a,&unsaturated
amides
unspecified
PhCOOMe
(73%)
including
by treating
to the
(lOO%),
u
NMe,
olefins,
valent
prepared
&ZHa
+
PhCH=CH,
conjugated
u
0
reduced
at all
alcohols and
, and
50-80° benzyl
acid
produced
to alcohols
aldehydes c4707. using
at 80-llO",
underwent
10
complete
reduction
Benzaldehydes,octanal
RuClz(PPhs)s
in benzene_ alcohol
a homogeneous
was
as a catalyst
Ketones not
and
aryl
hydrogenalized
and at nitro
277
2LiAlH(OMe),
+
CuBr
NaA1H2(0CH2CH,0CH,),
'" k THF
+
CuBr
"Li
complex"
"Na complex”
+
RI = R2 = H
Li complex
R'=H RI
/-L
84%
3 R2=Me989
R1 = R2 = Me
Rl
2 92%
0
(163)
0
R
RCH,CH&R
R
R'
R*
CO_$le -
Rlti
c4717.
Cat-ionic
to reduce
1 atmosphere, (prepared
in methanol
in very
high yield
hols,
which
although
corresponding saturated niclrel(I1)
alkynes
in some
cases,
to alkenes
methyl
presence
diphosphine p. 303
oxide,
acetoacetate
C4771.
and
as
catalysts
in methanol
at
aldehyde
only
the way
the
was
of ketones
with
at 40-65O,
lo-20
systems
reduced
modified
by the
addition
produced
a
to saturated
double
Similar
to alcohols
Acetone,
borohydride
saturated
boro-
were reduced
adamantanone
sodium
sodium
ketones
(NaOH).
all
in THF
with
reduced
base
aldehydes
Treatment
yield.
in toluene) which
reduced
used base
of Rh2H2C12(COO)(PPh3),PhCH,
strong
with
were
of strong
alco-
isolable_ bond
sodium
hydride/
hr reduced
olefins
The
to produce
ketones
to alkanes
and
[476].
nickel
of aluminum
effective
the
catalyst
E4757.
in high
Reduced
References
conjugated
acetate/g-amyloxide
to alcohols
halides
reduced
aldehydes
of
benzophenone
palladium
82%
presence
a catalyst
of nickel
97%
R1 = H3 R2 = Ph
hydrogen
presence
84"' ,'D
R1 = R2 = I&
Treatment
and
produced
in the
Reduction
catalyst
4737.
acetophenone,
2-hexanone,
duced
C472,
68%
of rhodium(I)
in the
CODRh(Cl)PPh3
hydride
C4741.
complexes
to alcohols
25°C
from
0
bipyridine
ketones
98%
R1 = H, R* = Me
OBe
-+
t/ RI
R = t-Bu R = ;h
to CH$ZH(OH)CH$OOMe
reduced
Rhodium(I)
catalyzed
the
the
optical
complexes
reduction
of
of tartaric
in 85%
yield.
containing a-ketoesters
Thus
optical Raney
the chiral to
chiral
acid yield.
nickel
reThe
was
less
pyrro:idine lactates
in
278 THF at 25O and 20 atmospheres [478].
Hydrogenation
rhodium
catalysts
3,17over
ketones
simpler
gave
cycl ohexanones,
less
bulky
quinones
to
[482%
alcohol
reduction
high,
with
olefin
reduction
ductively
of
it
lithium
LzNiCls,
FeCls,
source
hydrogenation
Mo(N2)(diphos)2
tertiary
by
isopropanol.
epimers
using
amine
carbony
rhodium
under
0x0
reduction
substantial
remained
or
complexes
alcohols
for
reduce
HsP(O)OH
rhodium(I)
aldehydes,
was
amounts
active
of
when attached
PhCH=CH-COzCHzCH-CHPhwas re-
of
the
palladium
or platinum
benzyl,
aryl
halides transfer
and
metal
have been by the
halides
CuI and ZnBr with
LiAlHJNiClz
material
TiCls,
VCls,
lithium
and LiAlHtJCoClz
aluminum
systems
re-
and aryl
bromides
in good yield
of
copper
hydrides
(LiCuHz,
LizCuH3,
prepared
by the
reaction
of
were found and
to reduce
tosylates
14881.
acetate
ZnCle,
MoCl s,
or zinc
ally1
halides
were reduced
to the
hydrogenation
lithium
primary
in moderate
WCls,
Mo(OAc)z
reduced
to hydrocarbons
hydrocarbon
from secondary
and nitrobenzenes
yield,
and
as well
cyclic
Cp2TiC12).
reduced
and secondar
C4891.
palladium
amines to
and
by
(Ni(OAc)2.
primary
by using
were
halide
cuprates
iodides
was reduced
and metal
chloride
alkyl
alkyl
to good
l-Bromonaphthalein
sodium t-amyloxide
ZrC14,
Halobenzenes
effected
transition
NiC12,
halides
cyclic
hydride,
CrCls,
organic
of reductions
the
CoC13,
chlorides
from nickel
[490].
study
low yield
sodium
reducing
tertiary,
LisCuHs)
yield,
of
catalyzed
for
work a series
in very
The reagent
that
secondary,
mixtures
alkyl,
to
to the more stable
excess
Finally,
aluminum hydride,
in excellent
fluorides
and
PhCH=CH-CHzCH=CHPhover
FeCls,
was found
In related
Aromatic
to
in THF/aq.
to ally1
The catalyst
[485x.
reduction
FeC12,
Li ~CUHL,. Li JuHs, with
and
was used
to cyclohexanols
specificity
unsaturated
new systems
the
primary,
[487%
source
by isomerization
In an extensive from
MnClz,
hydride,
With than
[4861.
developed.
duced
[480]. faster
by transfer
Aminophosphine
were reduced
was observed. polymer
A variety
resulting
on carbon
hydrogen
Rh2C12(CO)b
decarboxylated
in methanol
CrCls,
from
aliphatic
to an insoluble
5a-cholestan-3-one
reduced
to cyclohexanol
With cinnamaldehydes,
while
while
from cyclohexene
of cyclohexanones
aldehydes
prepared
conditions.
3-axial
same results
systems
palladium
t4831.
was accompanied
Conjugated
catalysts
the
gave
with Steroidal
of 5a-cholestan-3-one
36-01,
as the
catalyzed
t4847.
at C-3 to give
catalysts
over
as catalysts
The reduction
reduced
excess
yield.
in high
the equatorial
was reduced
MoHk(diphos)z the
alcohols
hydrogenation
hydrogenation
hydroquinones
a-phenethyl
enantiomeric
in isopropanol/HCl
c4811.
transfer
Cyclohexanone
using
axial
bul ky 4-substituted
substrates
Catalytic
gave
Platinum
in 36-764
cyclohexanones
In contrast,
catalyst
38-01.
axial
hydrogen
were selectively
C4791.
palladium
gave
of
unhindered
selectively
and 3,20-diones
hydroxy
the
of
chloride
as the benzenes
hydrogen and
amines respectively, by triethylarrmonium formate using palladium on carbon Nitrile and nitro groups reduced more slowly, olefin and as the catalyst. Ester, chloro groups were comparable, while bromides were the fastest. amide and ether
groups were tolerated
Nickel
reduced tri-
carbonyl
while
aldehydes
were reduced [491].
and dihalides to monohalides under mild Phase transfer conditions were used for the
conditions (eq. 164) C492Ij. dicobalt octacarbonyl reduction studies
were all
c4931.
Halogen was reductively
of a-bromoketones
aryl methyl ketones
except
eliminated
to ketones.
The ketones
for 1-adamantylmethyl
from haloalkanes
ArzCH-CXs w
ketone
by chromium(II),
ArCHCHZX THF
40-60%
(164)
copper(I) chloride
and tin(I1) with
C4941.
lithium
in 96% yield,
cyclododecanone
opened to the allene treatment
while
14951.
in high yield.
The acid
e-nitrobenzoyl
chloride
enones and dienones by treatment
were reduced
underwent clean (eq.
of chiral
to 80% ee (eq.
studied
and acetyl
with triethylsilane
aqueous isolation
166) C4981.
were benzoyl, furanoyl, hexanoyl, Cinnamoyl chloride and
1,4-reduction
[496].
to give
tetrachloride
Hydrosilation
Cyclohexenone
to
were ring
chloride.
and titanium
165) C4971.
rbromium(I1)
were reduced to aldehydes by anion in methylene chloride at 25”
in O-20% yield
rhodium(DIOP) complexes
hydrosilation followed anone, trihydrosilanes References p. 303
chlorides
of
a-bromocyclododecanone
1,1-dibromocyclopropanes
Acid chlorides ferrate
, e-bromobenzoyl
from treatment
reduced
with hydridotetracarbonyl
cyclohexanoyl
presence
The reagent
aluminum hydride
Conjugated
saturated
of a ketoesters
produced lactate
ketones
followed esters
by
in the in up
was reduced by LaRhCl catalyzed
by aqueous workup. Monohydrosilanes gave cyclohexgave 2-cyclohexen-1-01. while dihydrosilanes gave
280
enol ether
in 99% yield
octacarbonyl
cata7yst
plexes
by treatment
hydrazones
(85 references)
hydrazines
over palladium
reduced by cyclic
with phenyldimethylsilane and dicoba7t Hydrosilation catalyzed by group VIII com-
CSOOl.
has been reviewed Substituted
Cyclohexenone was converted to its silyl-
C4991.
mixtures of both products
C5017.
were synthesized on carbon C5027.
amines,
particulariy
by the hydrogenation of phenylAromatic nitro compounds were
indolines,
using rhodium trich7oride
0
+
00 I,
I!
R’-C-C-OR2
+
TiCl,
RsSiH
l
CRh7* + Ht
R3R4SiH2
H?O
&,CO,,R
PhH
I OH
R1 = Me, Ph
80-90% yields
R2 = n-F?-, nBu, i-Bu,
Et
30-80% ee
also 0
+“’
CH3 \
-
9
0
0 95-100% up to 84% optical or ruthenium trichloride halides
were less
as the transfer
reactive.
hydrogenation
Nitrosobenzene
was detected
yield
catalyst.
Pa7ladiur
as the inter-media:
Phase transfer conditions (benzene/aq. sodium hydroxide, benzyltriethylamnonium chloride) were used to reduce aromatic nitro compounds to
c5031.
the corresponding c5041.
anilines
The same chemistry
in 85-901 yields
by Fe(CO)s or Fes(C0)12
using 2-32 Cl87 crown-6 as the phase transfer
281 catalyst
was
reduced
also
nitroaromatics
compounds
reduced
converted
nitro
chain the
carried
out
to anilines
to the groups
deoxysugars
in 58-97%
aldehyde
in 32-77%
167).
The
of nitromethane
nitro
Chloronitrobenzenes
were
reduced
and
palladium
yield.
sugars
nitro
Titanium
of C-formyl
were
readily
protected
trichloride branched
available
glycosidulose
corresponding
on carbon
in methanol
Aliphatic C5067.
synthesis
the
to the
chloride
yield
in the
with
amines
by hydrazine
Chromium(I1)
to aldehydes
(eq.
condensation
[505].
from
[5077.
chloroarylhydroxyl-
[508].
(167)
Molybdenum acid
hexacarbonyl
solutions
to the
reduced
corresponding
tetrafluoroborates
decomposed
presence
catalysts
when
of copper
either
reductively source)
or Cl81
cleaved
and
Alkyl, with
copper
molybdenum
was
halides,
nitriles
and
nitro
by treatment
with
octacarbonyl
coupled
carbonyl
The
were
obtained
with
simple
were
unreactive
Pd were
verted
hydrogen As
compounds
c513-J.
C51.51.
of the
monoxide
was
p. 303
and
of
Co,
reduced
in the
was
Azoarenes
noted were
(hydrogen
at
were
was
[512].
reduced
olefins
reduced
to alkanes
Iron
presence
lost.
worst
The
(40%)
and
penta-
best
yields
obtained
sulfonyl
groups
of
in the
dicobalt
of tetra-
was
to mixtures
by hydrogenation
B-
presence
[516]. with
potassium monoxide
Mn
Ru,
Fe,
of
also
linear
OS,
Mn,
Cr,
a catalyst
to hydrocarbons to metal
compl'exes
to a mixture
Co,
to generate
(mostly
increased, increased alcohols
Ni,
which
Cu, con-
methane
the
same
esters,
whi?e
C5147.
in the
was
the
The reagent
ketones,
hydroxide,
olefins 145"
by treatment
This
epoxides,
epoxide while
yield
yields.
potassium
esters,
oxide
to sulfides
7595%
oxides,
the
of potassium
Fe and
in
in 88-100%
(95%)
Styrene
carbon
acid
to olefins
of graphite
ratio
reduced
and
Ketones,
with
[510].
were
to tetrasubstituted
complexes
Arenediazonium
fluoroarenes
No decomposition
present
Thioketones
pentacarbonyl
phenylacetaldehyde
treated
the
activity
References
acetic
phosphine
epoxides
and
C5111.
sulfones,
compounds
Pt and
cobalt).
in
alkyiepoxides.
and
not
sulfoxides
stereochemistry
rhodium
Laminar
on asbestos
them
C5091.
of arenes
crown-6.
was
by KaW2Cla
iron
in carboxylic
upon reaction with cyclohexene
withaketoepoxides
phenylethanol of cationic
Cl81
effected
deoxygenated
methylurea.
and
benzyl
compounds
N-carboxylanilines
crown-6
hexacarbonyl
transformation tolerated
and
nitro
to mixtures
to anilines
5% palladium aryl
aromatic
with
catalytic
15171. (methanol,
Carbon ethanol,
282
propanol and butanol) when treated Using
room temperature &187. solvent
at 180°
a 3:1
of
hydrogen
with
a catalyst
The use of
iron
pentacarbonyl
and alkali
and water
the water
monoxide A catalyst
[520]. sodium
iodide
gas shift
8.4
mnol of
hydrogen
7.6
mm01 of
carbon
168).
monoxide
amounts
2-methyl
of
and carbon
time
of
about
gas shift
[Rh(CO)zCl]z
giving
was consumed
phase
with
carbon
After
monoxi
45 hr,
were produced,
while
platinum
in acetic
acid
and exo-2-methylnorbornane
reactions
[522].
a day.
over
7-methylnorbornane
vapor
acid
C5211.
3-methylnortricyclene
compounds
with
was investigate< acetic
at 400 nm~of
dioxide
C519-J.
olefins
reaction
cycles
carbon
was converter
minutes
in glacial acid
nine
mnol of
monoxide
lo-15
to hydroformylate
hydrochloric
catalyst
of
In contrast
most
of
and 8.6
Hydrogenolysis equal
via
and concentrated
was a water
gave
turnover
consisting
as a catalyst in molten NaCl-2AlC
Ir4(CO)1z
mixture
to alkanes carbon
(Me2CHCH2)2AlH and CPnZrClz at
with
over
Similar
supported
reactions
of
metal
the
(eq.
catalysts
cm\
propellanes
tricyclo[4.4.1.01~6~undecaneandtricyclo[4.3.l.01~6]decane
were studied
[523-j.
Lb
Me
Benzyl
ethers
from indoline
were hydrogenalized
using
rhodium(II1)
palladium(I1)
chloride.
hydrogenalized
these
by treatment
catal>
amount of
‘ic
[5261,
Functional A.
[525].
metal
catalysts
by alloys
addition
of
iodine,
halides
cyanogen cuprate
halides
of
has been reviewed
and few side
halides
ring
prepared cuprates with
and cyanogen [528].
presence
of
a
carbon-carbon
(18
references)
clusters
0271.
products
in 74-90X
regio-
to terminal
iodide.
Aryl
alkynes,
were convert
N-chlorosuccinimi,
The stereochemistry
amines
were converted
and copper(I1)
were obtained
and stereospecif
in this
to
halide.
reaction
of
the
aryl High
with
fifteen
The following functional groups were tolerated
by this
Under similar
by the
N-bromosuccinimide,
with t-butylnitrite
substrates.
in the aromatic
alkyl
by treatment
bromide
by treatment
Me c5297.
cuprates,
was retained
representative
aryl
were hydro-
in the
The hydrogenalysis and bimetallic
were also
alcohols
chloride
and
Group Preparations
bromomagnesium
ed to vinyl
yields
Ally1
hydrogenation
acetate
Hal ides
Bromomagnesium vinyl
vinyl
propylmagnesium
L2NiCl2
supported
r-5241.
(168)
by transfer
palladium(I1)
and B-phenethylacetate
conditions
with
as has catalysis
V.
to toluene
chloride,
Benzylamines
under
genalized bonds over
$ +&
H;;c +
reaction:
conditions yield.
NOz, MeO, COOH, Cl, aryl
A range
of
hydrazines substitution
F, CFs, H and
were also patterns
converted was
to
tolerated ethyl
deamination
out in the presence acrylate
(eq.
When this
C5307.
carried
and styrene,
169) 15317.
than they
aryl
The yields
halide
RON0 CuC,, + MeCN
AX
by A-butylnitrite
was
such as acrylonitrile,
added to the conjugated
were considerably
the Meerwein reaction
were using
ArNHz +
of arylamines
of Michael acceptors
better
using
olefin
this
procedure
(ArN2).
ArCHzCHX ;1
(1691
X = CN, COOEt. Ph Ar = e-NOzPh (93%), g-N02Ph (74%), e-MeOPh (83%), E-ClPh (81%), p-MePh (73%),
2,4,6-ClsPh
Alkynes were converted than 80% yield
to mixtures
by treatment
in acetonitrile
(92%),
(eq.
with
2,4,6-(MeO)sPh
(0%)
of E and Z vinyl
copper(I1)
170) [532].
dihalides
chloride
in greater
and lithium
Chromous chloride
(170)
E 95%
95:5 E:Z
Z R = Ph, R’ = Et
R = Ph, R’ = Me 94%
98:2 E:Z
R = Ph, R’ = t-Bu
R = Ph, R’ = H of N-haloamides yield,
also
1-Octyne
urethanes
chloride
promoted the addition
CuCl ?-Li Cl MeCN
RCXR’
in fair
Ph (71%),
to olefins.
N-Chlorocarbonates
but cyclopentene
reacted
gave
in low yield
to conjugated
dienes
only
(eq.
was also
94%
95:5
95%
21:79 E:Z
added to steroidal
20% yield
171).
of
addition
The addition
studied.
Both 1,2-
E:Z
olefins
product.
of N-chloroand 1,4-addition
occurred [533]. The reaction mechanism was studied and was shown to go via a radical chain pathway [534]. The complex (CO)kFeNMe3, prepared from trimethylamine tetrachloride
and iron pentacarbonyl,
to olefins.
ment as well chloride
oxide
Bridged polycyclic
as addition
in a 2:l
(eq.
mixture
predominantly
cis
60-708 yields
C5361.
open epoxides
to trans
Ferric than
completely
general.
Stilbene
References
p. 303
C5377.
the addition
with chromyl
oxide was rearranged
to produce
of regioisomers
in ether was an efficient in high yield.
of carbon
underwent rearrange-
reacted
and acetylchloride
as mixtures
HCl or magnesium bromide.
or better
reagent
chloride
chlorohydrins
be as good
by this
acetates
olefins Olefins
172) [535].
of dichloromethane
chlorohydrin
catalyzed
in
reagent
It was claimed
to
However, it was not to diphenylaceta?dehyde
to
284
RO-C-NHCI Fi
+
NHCOOR 79%
f
cc1
(CO),FeNMe,
ClsC
I+
1
90% I
and
j/j&
(172)
-OF ClsCCH, 80%
B.
Amides, Nitriles
Terminal
acetylenes
underwent
a regio- and stereospecific cis
addition of alkylcopper halide/magnesium
halide complexes to produce ter-
minal vinyl cuprates which were converted to substituted acrylonitriles by treatment with ClCN, PhS02CN C538J.
or TsCN in greater than 90% yield (eq. 173)
Cyclic ketones were c!eaved to w-cyanoesters by treatment with
NasFe(NO)CNS
(es. 174) L-5391. An angular nitrile group was introduced
into decalin systems by conversion to iron cyclohexadienyl cationic complexes and treatment with sodium cyanide (eq. 175) C5407.
The addition
of hydrogen cyanide to olefins has been reviewed c5417.
LWI R
R-CaCH
+
[R'CuXxgHal
-+
H
MgHal
-
I
cux
-
YCN
H
R
(173) R'
N >90%
/-COOR NaqFe(NO)(CN)< f
[complex]
Hi, ROH 'YLCN
I n = 3, 4, 5 1
10% NaOH
(&"OH
l
A
('74)
cCH=NClH
(175) Fe(CO)s
Fe(CO)s OMe
f
OMe NaCN HZ0
(8F,)-
&
l
I &
C.
:
CN
43%
80%
Amines
(S)-Glutamic acid was synthesized in 100% yield and 10-46X optical yield from methyl acrylate,sodium
A-bis[N-salicylideneglycinatolcobaltate(III)
and sodium A-~CN-3-methylsalicylideneglyicinatolcobaltate(IIi) 'Diastereomeric complexes were formed and electrochemically
Styrene,
l-octene
N-alkylaziridines followed C543J.
and cis-2-octene by treatment
by an oxidative Olefins
were converted
at pH 11.4.
reduced [542].
to the corresponding
with a primary amine and palladium
cleavage
were diaminated
(Br2)
of the a-alkylpalladium
by osmium-imine complexes
(eq.
chloride
complex 176) C5447.
Primary and secondary amines were converted to secondary and tertiary amines by alkylationwithalcohols and Raney nickel (eq. 177) C5453.
in the presence of tri-t-butoxyaluminum a-t-Butyloxy- and a-acetoxyacrylonitriles
were converted to imides upon treatment with ferric chloride in acetic anhydride
References
(eq. 178) [546].
p.303
286 \’ -
1) CClL 2) LiAlH,+, 3) i&O
-I-
P R
Et20
(176)
l
or
2
76% R' = H
63%
'
RI,
(tBu0)9Al RaNi
R30H
f
R2' R1 = ph-
89%
R = n-octyl.
CdoPMe
NH
, R'=H
R = R' = n-Bu
/4'+,+
+N
Me0
R=Ph
//N-t
0\
R2 = H, Me;
Rl 'N-R3 R2'
'
(177)
34-98%
R3 = n-pr.i-pr
-;CH2)5-
CN
’
OtBu
NC
(EtO),;' 'OtBu
l
FeCl? Ac20
I x R
l
R
(178) n
NH
Me
D.
Ethers,
Methanol
added
acetylacetonate,
in 98% yield. c5471.
1,4
sodium
to methacrylic hydroxide,
of a platinum(I1) conditions
by potassium acetate
esters
in the
triphenylphosphine
presence and
of
(eq.
acetylated olefin
179)
complex
CSL.87.
peroxydisulfate/acetic
complexes
as catalyst
alcohols
was
The
in 50-100X
as catalyst mechanism
acid studied
with
nickel(Ii)
triethylaluminum
With base but no nickel salts, only 30% yield
N-Acetylimidazole
sence mild
Esters
was
yield
in nonpolar
of aromatic
obtained
in'the media
preunder
acetoxylation
2,2'-bipyridine/palladium(II)
[549].
287
R’ (CHz)n-;-OH
+
PtC1T(C7H~) 3
N-acetylimidazole
ril
(179)
R’ n = 1, 2, 3, 6
-;OAc
R = H, CHs
RI
R’ = H, CH,
50- 100%
E.
Heterocycl es
Two new approaches
and isoquinolones
to the synthesis
esters
produced substituted
2-acetonylbenzoic
sodium hydride
in t-butanol
Alternatively,
reduction
(eq.
180).
P-bromobenzoic
acids
acids _
Cyclization
sodium carbonate. upon reaction
esters.
produced
The other
Isoquinolones
halides
were prepared
lactones
acetylene
insertion
8-methylene-&lactones presence
acid,
and acid
hydrolysis
Oxidative
cleavage
cyclopropanone
chloride
of the copper in low yield
reacted
oxiranes
reacted
reacted
182) [5517.
C5521.
in fair
yield
184) C5.547.
(eq.
Ring openin
of
in the
yield
iron and cobalt
(eq.
catechol
of titanium
185) C5557.
cata7ysts substituted
in refluxing
tetrachloride,
183) [5537.
Mixed silylketals
in the presence
A cyclohexadiene
with copper acetylacetonate
intra-
produced a 6-keto-v-trimethylsilyl
in excellent
while
786) [556].
ides
and carbon
chloride
complex of 3,5_ditertiarybutyl
(eq.
(eq.
The mechanism
alcohols
with carbon monoxide and rhodium catalysts
6 lactones, (eq.
fashion
and
to 2-buten-4-01
with an aldehyde, titanium
with aldehydes
to give y-lactones
6 lactones
catalyst
of
chloride
agent was found to involve
gave pentenolides
chloride
unsaturated
(eq.
during cyclization
which upon treatment
produced a lactone
in a similar
by trimethylsilylmethylmagnesium
of a nickel
carboxylic
by palladium
from acetylenic
monoxide using Pd(PPha),, as cyclizing molecular
of the reaction
were cycl ized
chloropalladate
yield.
to produce 2-allylbenzoic
was effected
carboxyl ic acids
of a-methylene
in excellent
produced the dihydroiso-
approach consisted
to isocoumarins
of substi-
bromide in DMF
Treatment of these with
isocoumarins
hith s-allylnickel
with lithium
of preparation
with n-(E-methoxyallyl)nickel
by sodium borohydride
Unsaturated
181) [550].
dihydroisocoumarins
Treatment of a variety
have been developed.
tuted E-bromobenzoic
coumarins
of isocoumarins,
xylene
of tetraVinyl
to give
e,y-
give a,B-unsaturated diazoacetylacetonate to give
a polycyclic
288
e COOMe
OOMe
k
Br
o
X
(180)
COOH
FOONa
I R * X 0
60-80%
(18’
X also
+
0
PdC12
+
NaH
+ OH 68%
289
RCH=CHCH2COOH
Li7PdC11, H20
0 32-38%
(182)
R RCH=CH-CH2CH2COOH
+
Me7SiCH7MgCJ NiCJ,cataJyst '
Me3Si&ooH
+%j%i=+
95%
\ A
(183)
R
fair yield
(134)
lactone in excellent yield (eq. 187) [557]. Certain hydroxyacid salts of rigid conformation lactonized rapidly in the presence of copper and zinc(I1) salts C5587. Chiral 4-alkyl-y-Jactoneswere prepared from alkenyl g7utamicacidenantiomers by a sequence which involved organocuprate alkylaReferences
p. 303
290
EtG
0SiMe3
X
+
TiCl,
RCHO
-f
l
(185)
Rh(I)
~
75% RI, R2, R'-6 = H R3 = Me
R&
\ 3-
1
+
I
R4
co
~
(186)
R6
R5
R3
1
Fe,Co
RL
R2
R5
f-
'. RQ % R3 = alkyl favors lactone
R6
R5 = COOMe -f loss of CO2
R1, R6 = alkyl + acyclic ketones
tion of a tosylate of the la&one
without ring opening (eq. 138) C5591.
1-Hexyne reacted with carbon dioxide in the presence of Ni(CODj2 and chelating diphosphines to give 4,6-dibutyl-Z-pyrone
in lovtyield C5601.
291 ,OMe
(187)
H 71%
Oxidation
of P-hydroxyalkylfurans
with
pyranones
in high
C.5617.
yield
some
chloro-n-allylpalladium
(eq.
190)
(eq.
189)
chloride
pyridinium Carbon
chlorochromate monoxide
complexes
gave
reacted
to produce
hydroxy-
with
butenolides
C5627.
(188)
RcH2fro oyridine chlorochromate
R = Ne,
n-hexyl,
ACH
(189)
2
CH3
Cl co MeOH/CHZC12 8 hr
Ph
Ph h
'
Ph
Me Azirenes acetonate
reacted
to produce
with
ketones
pyrroles
in the
presence
in quantitative
Diphenylazirenes
reacted
with palladium(II)chlo
without
at
to produce
References
catalyst p_ 303
170"
indoles
(190)
\
yield
0
of nickel(I1) (eq.
191)
catalyst quantitatively
acetyl-
[563]. at 30°
(eq.
141)
or C5641.
292
Carbazole
was prepared from phenothoazine
and 2,2’-bipyridyl reacted
in 60% yield
with a catalytic
(eq.
by desulfurization
193) [565].
with (COD)zNi
N-Allyl-2-bromoacetamides
acetate, triphenylphosphine and A similar procedure with TMEDAin DMFat 125” to produce N-acetylindoles. N-ally?-benzylamines Annelated
gave isoquinolines
pyridines
of a,o-diynes
amount of palladium
and nitriles 0
+
in low yield
(eq.
194) [566].
were prepared (eq.
by the cobalt catalyzed cooligomerization Pyridones were prepared in a 195) [567].
Ni(acac):, 25”
R3CHz;-R4
(191) H quantitative
R1 = H3 Me, Ph R2 = Ph Rs = COMe. COPh, CN, COOEt R4 = Me, Ph
Ph Ph
R
Ph
PdC17(PhCN)7 catalyst 30’
(192)
R quantitative
170”
R = H, Me, Ph
similar
fashion
products
from alkynes
resulted
with isocyanates treatment carbanions
and isocyanates
from treatment (eq.
197) [569].
Isoquinoline
of P-bromobenzaldehydein the presence
condensed with silyl produce a-lactams were aminated,
(eq.
cyclopentadienyl
then oxidatively
cyclized
The same
cobaltacyclopentadiene were produced by
oximes with stabilized
bromide (eq_ 198) c5701.
in the presence
in 40-90% yields
approach to 0-lactams,
196) [568].
N-oxides
or -acetophenone
of copper(I)
acetals
(eq.
of the intermediate
of titanium
199) [5717.
iron olefin (eq.
Imines
tetrachloride In an elegant
cationic
200) C5721.
complexes Copper(I1)
to
aBr +BFcoone +
~>cooMe
NHAc
N AC
CCOOMe 25 Pd(OAc)? 2 Ph,P TMEDA 125=‘, DMF
73%
AC
also
(194)
Ph f
/--=CH
7
cpco(col high
’
(car
l
di 1 ution n = R =
n-Bu,
3, Ph,
4,
n = 3,4
5 Ye,
(195)
CH20Me,
COOEt,
CH2COOEt,
CH2CH2CN,
C,F,,
t-Bu FooEt
with
References
R = CH2COOEt
p. 303
and
excess
RCN
-f
294
acetylacetonate type
rearranged
B-lactams
(eq.
penicillin
type
C5731.
201)
to
B-lactams
cephafosporin
R R’
+
RC-CR’
i = Ph,
R”NC0
Me,
R’
= COOMe,
R”
=
“Co catalyst” PhH, 135” 2 hr
nBu, H,
r
+ 0
(196)
H Ph,
Me
R’
Ph , Me , nBu
R5NC0
-
(197)
R4
40-80% (from
alkyne)
same
NOH
R’s
+
as
in
eq.
R2CH,COOEt
196.
NaH/CuBr/Ph:i
(198)
R’ R3
R1 = t;,
Me
R2 = COOMe,
COMe,
R3 = RL’ = H , 0-CH2-0
COPh ,
COOEt , CN
295
R’CH=NRz
,0R5 R3R4C=C ‘OSiMe3
+
R1 = Ph,
i-Pr,
R2 = Ph,
PhCH2, Me
TiCl, CHzClz
base
l
(199)
l
Et
R3 = R4 = Me,
40-90%
(CH 2 ) 5
R5 = Me
CCpFe(C0)2((7’
+
-25”
PhCHzNHz
r
/ 1 PhCHzfH2
1) Cl?, -78O 2) Et3N
\ FeCp(CO),
C”3
(200) and
A
9’3
*
(CH24,
Chlorodibenzofurans with
palladium
acetate
densation
of
223”
202)
(eq.
cyclohexanone steps
Refuel;ces
iodoarenes C5757. in
e-methylfurans
unsaturated
p. 303
were
cyclic
the
formed
[574]. with
by the
Dibenzofurans
presence (eq.
were
of
203)
to
The iron
butadiene
diphenylethers
formed
by the
by copper
condensed
(MeO)sPCuI
[,576].
from
of
also
2,4-dimethoxyiodobenzene
Diazodimethylmalonate
peroxides
cyclization
after
catalyzed
produced
furans
powder
at
enol ethers of
with
produce
con-
several
other
decomposition in
high
yield
of
296
(201)
THF
cu(acac)7
F 43%
(eq.
204)
with
a,a’-dibromoketones
route
to
t-5777.
muscarines
cyclization in
high
Diiron enacarbonyl effected the condensation of amides
of yield
tyiacetone
1,4-diols [579].
via
to (eq.
produce
205) to
furans,
A bridged
a platinum
Palladium
chloride
and 1 ,Spentanediol
bicycliz
complex
This
3(2H)-furanones.
[5781.
(eq.
triether 206)
was used as a catalyzed
to
the
tetrahydropyran
was produced
from
ace-
[580].
OMe
OMe
HBr
Cu powder 220°
ile
+
N2C(COOMe)2
+
(MeO)aPCuI
-
Me
(203)
1) NaH 2) LiAlH, 3) H+
‘0 +Ir? 72%
e ‘.
297
I
crc;“:
I
IO
NO
FeS04 aq. THF
’
\
\
\
quantitative
(204)
Br
Br
0
R '_ Fe3(C0)k
l
(205)
NMe,
R = Me,
Et,
i-Pr,
R’
Me,
Ph
= H,
+
t-Bu
30-90x
K2Pt6rL
-
--
NaCN
References p. 303
KOH
O\
,CH(COCH,),
O/ptNCH(COCH,),
+
HC’
(206)
298
Imidazolones chloride aniline
assisted
and iminoxazolidines
were prepared
reaction
with a-aminoesters and 2-hydroxyr-Allylpalladium chloride reacted
respectively
with 1,3 dipolar
(eq.
f
297) C581].
by the palladium
species
Ph&N=N-Ph tc give both the dimer and the ally1 The ally1 adduct was thought to occur via species.
adduct of the dipolar
+-NC
of isonitriles
PdCl 3
R’CHCOOEt
(201
N-+
AH2
R’ = Me (42%);
PhCH2 (80%);
i-Pr
(82%);
set 5u (70%)
+
-f
also
+
-/-NC
+
Ag,O
PdCl,
84%
generation
of ally1
cycloaddition
chloride
followed
to the palladium
by cycloaddition,
complex itself
cycles were available from the intermediate isonitriles with dicobalt octacarbonyl (eq. dimerized other
upon treatment
heterocycles
209) C5841. dicobalt (eq.
Azobenzenes
210).
Yields
[I5821.
than by
A variety
of hetero-
produced from the reaction of 208) [583]. Phenylazirenes
with chromium, molybdenum and tungsten
were available
octacarbonyl
rather
reacted
by slight
variation
with isonitriles
reported
[585-J.
carbonyls.
scheme (eq.
in the presence
to produce 6H,12H-indazoloC2,l
were not
of this
of
,a]-6,13-diiminoindazoll
Oxazoles
were synthesized
by
the tungsten hexachloride decomposition of a-diazoketones in the presence of nitriles (eq. 211) [586]. Isoxazolidines were formed in the reaction of oximes with butadiene 212) [I5871.
and palladium
Reactionsoforganometallic
has been reviewed
(7 references)
[588-J.
nitrate-triphenyl
phosphine
compounds in the heterocyclic
(eq. field
299
NP t
NC
CO2(CO)8+
9o”
‘WCNR)
(RNC) ,Cd
l
Y R/N
R-Q-J\ R = H, R’
= H,
OMe, CHO,
3
M(CO)E, ;“,:
(208)
>
R’
60%
Me C=N-Ph also
(209) tiHo
-
s
80% ‘0
67-863
?
Ph
(210)
X NR References
P_ 303
Miscellaneous
H.
Allylphenyl and benzylphenyl Ethers underwent carbon-oxygen bond cleavage
upon treatment
zero
Similarly,
and Ni(PEt,),C5897. SiMes,
with
valent para
nickel
complexes
substituted
(H,
Br,
CMe=CH2, CH2CH20Ac, COOMe, CHOAcCHs) benzylallyl
N III c
+
such
as (COD)zNi
Me, OUe, Cl, ethers
were
cleaved
(217 1 Irlcl=
R
l
i 50-66% R = Ph, Me, Et,
vinyl
(212)
63%
to
the
corresponding
homogeneous
para
RuC12(PPha),
mixture
of
glyrol
dioxide
and hydrogen
hydrolyzed
lo3
*and cobalt(II), Cyclic
mono-
to
at
lo5
catalysts
(es.
213)
benzaldehyde
as a catalyst and diformates 100”
faster
compared
hydroperoxides
substituted
to
were
c5907.
Epoxides
and 40 atmospheres
the
hydroxide opened
64-83% yield
by RuC12(PPh3)a
when catalyzed
ring
in
[591].
Imidazole
a
esters of
hydrolysis ketones
to
carbon
species
mediated
conjugated
cleaved
catalyst,
by hydroxo ion
to
were
using
nicke7(II) [5921.
by palladium(I1)
C5931.
c% R
Pd( II)
OOH
+
(CHz),,
R=H
n = 1,
R=Me
n=2,80%
75%;
n
2,
50%;
n = 3,
35%;
n = 4,
20%
HZ0
(213)
301 Dimethyl
diazomalonate
copper
salts
chiral
sulfoximines
were
to
replace
converted
AgTFA,
A and
by treatment
with
cyanates
by treatment
214)
the
115981.
f
R = o-ClPh
Treatment
produced
copper(I)
sodium
Other
asqualene
to
Ph
with
be a good
solution
iodide
were
prepared
in the
carbonate
allylic
to give
alcohols
RNH-C-NHR
also
(214)
EiTs
(57:;), cyclohexyl
anhydrous
procedure
of chiral
penta-
selenocyanate
iron(III)
(66%)
for
in dry
chloride
1,2.5.6-di-o-isopropylidene-o(-D-glucofuranose)
was claimed
iron seleno-
[599].
(86%),
of glucose
or
2-bromothiophene
and
of
to X-tosylimino-
ferric
with
iodide
(Hg(TFA)*,
to aryl
using
Using
synthesis
thiocyanates
in 77% yield.
fashion
o-MePh
and
reacted
1) Cu or Fe(C0)5_ rfx CHCl, 2) aq. HCl
(72%),
100”
at
yield.
salts
of copper
converted
of
Thioesters
converted
by aqueous
sodium
in 40-603
metal
were
presence
15947.
in a partial
presence
HMPT
alcohol
Z-thienyl-CH,CH,CHO
TsNs
with
were
followed
acetate,
in a similar
RN=C=NR
in
group
used
selenocyanates
Ally1
of palladium
aldehyde
reacted
Alkyl
in the
in the
retention
was
iodides
KSeCN
by hydroboration
or thiocyanate presence
with
Carbodiimides
Aryl
with
sulfoximines
by treatment
tosylazide
[596].
C5971.
olefins
went
conversion
B [5?57.
(eq.
as a catalyst
This
with
by the malonate
reaction
AgBF,).
carbonyl
from
oxygen
the
to t-butylesters
CuTFA,
cytochalasins ureas
reacted
acetone
in 82% yield.
making sugar
co, /”
acetonides
was
used
c6007.
as a liquid
This Finally,
phase
CONRh\O
for
the
separation
Quantitative
of the
resolution
two
enantiomers
in 3 hr at 27"
was
of 3-methylcyclopentene. reported
[601].
Reviews
VT _A.
The
following
"Preparations
of Highly
Organometallic "Titanium "Recent
reviews
theses
Reactive
Synthesis"
Metal
in the
have
appeared:
Powder s and
Their
Synthesis"
Organometallic
(59 references)
Chemistry
of Titanium"
C6047 "Low
Valent
References p_ 303
Titanium
Use
in Organic
and
C6021
in Organic
Tetrachloride Advances
and
in Organic
Synthesis"
(thesis)
[605]
[603] (21
references)
302
“Organic
Synthesis
“Organopalladium “Selective
via Metal Carbonyls” Intermediates
(book)
[606]
in Organic Synthesis”
Organic Transformations
(279 references)
via s-Allylpalladium
(-6073
Compounds” (thesis)
t6081 “Organic “Recent
Synthesis
with Palladium Compounds” (157 references)
Progress
in Organic Synthesis
(126 references)
using Iron Carbonyl Complexes”
c6101
“Organic
Synthesis
with Iron Carbonyl”
“Organic
Synthesis
with
“Reactions
[6091
of Olefins
(197 references)
Tetracarbonylferrate”
(43
c6111
references)
[6121
with Palladium and Rhodium Complexes”
(7 references)
C6131 “Organic
Synthesis
“Me’:al-Carbene
Using Transition
Metal Compounds” (19 references)
Complexes in Organic Synthesis”
“a Anions of Metal-Carbcne
(~150 references)
Complexes in Organic Synthesis”
c6141
[6151
(61 references)
c6l61 “Arene-Metal “Organic
Complexes in Organic Synthesis”
Syntheses
via Allylic
(55 references)
[6171
Complexes of Metal Carbonyls”
(300 referent
C6181 “Transition
Metal
“Cyclometallation
Reactions”
“Ortho-Metal lation “Heterogeneous “Catalysis
in Organic Synthesis”
Hydrides
Reactions”
Catalysis:
(133 references)
II6213
Reaction”
(63 references)
(34 references)
“Free Radicals “Transition
in Organometallic
“Catalysis
Chemistry”
(298 references)
of Symmetry Restricted
(93 references)
Catalysis
and Organometallic
(195 references)
C6301
C6267
Compounds” (285 references) Metals“
(156 references)
of Phosphorus Ligands in Organometallic
Homogeneous Catalysis”
Metal Complex
c6251
Metal Complexes of Olefinic
Effects
Transition
[624]
“Organoni tri le Complexes of Transition “Steric
[622]
A Bridge Between Homogeneous and (20 references) c6231
“Development and ApplicationsofHomogeneous Chemistry”
(38 references)
Complexes:
Catalysis”
“How Asymmetry Might Be Induced in the Chiral Catalyzed
[6l9]
[620]
Some Recent Developments”
by Polynuclear
Heterogeneous
(157 references)
(thesis)
L-6277
c6281
Chemistry and
c6291
Reactions
by Transition
Metal Compounds”
303
"Coordination in Applied "Activation "The
of Alkanes
Homogeneous
"Mechanism Metal
Heterogeneous by Transition
Catalytic
of Oxidative
Complexes"
Catalysis"
(49
"Cyclobutadienylmetal
Metal
Activation
of
Compounds"
of Organic
references)
[634] (355
(102
Carbon-Hydrogen
Addition
Complexes"
(90 references)
Halides
references)
C6371
references)
Bonds"
to Group
[632]
[633]
8 Transition
[535]
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