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Lithium
I
LITHIUM At:l’iUAL SURVEY CO’IERIKG THE YEAR I976
EDWINM. WISER
Department of Chemistry, Missouri 65201 (U.S.A.)
University
of Xissouri-Columbia,
Columbia,
COF:TE:!TS I 2
Reviews and Books Structure and Bonding Studies Kinetics and Mechanism 3. 4_ Metalations A. At sp3 Carbon 6. At sp2 and sp Carbon and at Nitrogen Lithium Carbenoids and Other Halogen-Substituted Organolithiums 65: Addition and Substitution Reactions 7. Heterocycles Copper-Lithium Reagents and Other “Ate” Complexes 8. Lithium-Halogen Exchange Reactions 1:: Reductions and Radical Anions 11. Reactions with Inorganic and Orqanometallic Compounds 12. References 1. 2.
1.
:: 21 31 35 37 43 5% :: 68 78
REYIEWSAND ROOKS Reviews and chapters
lithium
chemistry
in books devoted
included
- 13C XMRof organolithium - Fast reaction
studies
- Use of lithium tron-transfer thesis
process
- Annulation - Syntheses - Preparation
(1977)
or in part
to organo-
[1,2]. in solution
addition
reactions
c31. as models for an elec-
[4]. in the use of organolithium
reagents
in organic
syn-
preparation
and synthetic
uses of
ketone enolates
[6]_
[7]. of caretenoids of alkenes
[8,9]. from tosylhydrazones
Annual Survey covering l-131_
wholly
[S].
- Regiospecific
Lithium.
reagents
of carbanions
organocuprate
- Recent developments
either
the following:
the year
[lo].
1975 see J.Organometal.Chem.,
130’
2
Recent methods forthe
synthesis
of polyfluoroaromatic
Preparation
and chemistry
of unsaturated
Nucleophilic
substitutions
at acetylenic
- effects
Allopolarization tiona?
anions
carbon
of substituents
acylation
[13].
on the reactions
reagents
Metal-ammonia reduction compounds [18].
and related
reactions
solvents
in organic
synthesis
Boranes and heteroboranes
[23]_
Metalloborane
with ligand-metal
derivatives
metals
plexes
in organic
synthesis
single
bonds [24].
[25].
nucleophilic
aromatic
substitution
metals
[26].
in :-arene-metal
com-
[28].
Transition
metal dialkylamides
- Gold chemistry
organometallics
metal derivatives
- Preparation
and disilylamides
[29,30].
[31]_
- o-Bonded actinide - Alkali
carbonyl
[19,20,21,22].
c-Alkyl and -aryl complexes of group 4-7 transition Metal-carbene complexes in organic synthesis [27]. Metal assisted
[17].
of =,%unsaturated
_
complexes
Transition
of ambifunc-
[15].
utility of P-oxazolines [16]. of alkali metals in ammonia and other
Boron “ate”
compounds [ll].
[12].
[14]-
Nucleophilic Synthetic Solutions
lactones
of chiral
of tin
[32.33,34-j. [35].
trioganotin
halides
using
organolithium
reagents
[361- Preparation - Inorganic and other 2_
of new homoleptic five-membered hetero
elements
and amides [37,38].
systems consisting
X-ray diffraction
nitrogen,
[39].
has been employed to determine
of dilithiated
(TMEDA) (Fig_
stilbene
the hydrocarbon
to one another.
The lithium
portion
atoms chelated
above and below the midpoint
bene molecule.
The stilbene
~-delocalized other
carbanion
than disolvated
and crystal
bis(lithium
2) [40].
PMDTA)structure atoms_
rinss
by the amines are located
of the olefinic
complex to be isolated lithium
(PMDTA) (Fig.
is planar with the aromatic
equal distances
contains
the molecular
complexed with tetramethylethylenediamine
1) and with pentamethyldiethylenetriamine
In each structure,
first
of silicon,
STRUCTURE AND BONDINGSTUDIES
structures
trans
alkyls
ring
at
bond of the stilis said
to be the
and so characterized
which
Solution
X-ray scattering
have been used to determine diethyl
ether
distance
solution
is estimated
most probably
as structure
the authors
of 1 with methyl iodide, and accounts
reactions.
paper,
In another
in dimethyl
for
its
I Li
I Li
I
I
I
that
LiCu2(CH3)3 (2),
ether of LiCu(CH3)2,
I Li
the dimeric
struc-
in Corey-Posner to show the ore-
and Li2Cu(CH3)3
(3)
[42].
3
CH3-Cu-CH3-Cu-CH3
CH3-CL.-CH3
A la;-ge number of other study organolithium
publications
First,
reagents.
of R- and racemic
structure
The copper-copper
unusual reactivity
I_
fine
1 [41]-
and ‘H h?tR as a dimer in
‘H NMRhas been employed at -136”
CH3-Cu-CH3-Cu-CH3
spectra
exists
conclude
CH3-Cu-CH3
i’
depression,
dimethylcuprate
fi and the methyl groups are either equivalent Based on kinetic studies on the exchange even at -60”.
ture of 1 is important sence
vapor pressure
to 4.420.7
or undergo very rapid reaction
methods, that lithium
also
line
shape analysis
2-methylbutyllithium
as a result
of chemical
described
shifts
‘H !iHR to
the use of
in 300 FTHz‘H NFlR
hexamers in pentane has revealed among diastereomeric
aggregates
The spectra of the racemic reagent indicated 1) an inversion at carbon c433. bonded to lithium which occurs within a hexamer aggregate and 2) an interaggregational
exchange
of organolithiuas
In constrast,
the R-lithium
the inversion
process.
processes
reagent
showed a line
The heats and entropies
inequivalent
sites.
shape chanqe ascribed
of activation
for
only
to
the two
are listed.
The unstable by metalation as evidenced
lithio-Z,E-1,3-diphenylallyl
by XMRspectroscopy
and the following tl,2(-30°)
values
on its
are recorded:
The later
in similar
(4-Z,E)
and by reduction
of
perdeuteratedphenyl
of 4-Z,E to the more stable
= 2-g min. 4-Z,E
anion
of cis-1.3-diphenylpropene
rate of isomerization
observe
between magnetically
5 by lithium derivative.
4-E,E was followed
tit* = 17.321.8
value explains
has been obtained
kcal/mol.
why previous
The by RR.9
~55. = 2.028
workers
failed
studies.
r
Li+
7
bh
. I!3
4-Z-E
A ;
H\&+/Ph
H
Ph
Ph
H
5
metal
4-E,E
e-u.,
to
Several studied
9-aryi
by both
magnitude of ring bered ring tuents
[45].
9ave linear
nhich
ho;;roaronatic
based on SIR alone
Metalation annulenyl
theory
conclud?
that a ring
that paratrclisn magnetic
results
dipo?e
that one might conclude compound [46]_
without
a caveat also
Since
is issued
considering
cur-
of the ‘:.M-LUYO energy oao. frop
low-l:/ing
transitions.
a suffi-
that 7 is a completely
earlier against
stabili:ies
work had demonstrated reaching relative
such conclusions to an aopro-
compound_
7 of hydrocarbon systei
data _ This anion ion e;:hibiting
of the eight-men-
P
the authors
is a function
8 9 by c-butyllithiun
11, whose ‘H iMR was compared to that of [13]
shifts
(6) were
groups on the
of the ‘i! WR spectrum of 7 with that of 9 reveals
number of similarities
reference
the chemical
through allowed
that 7 is not homoaromatic, priate
styrenes,
the current
accessible
A comparison delocal iced,
Since
anions
of such aryl
with the tr values of the phenyl substiP the trend of >max values relative to ? !r opposite to that
support
states
the effect
plots
is being observed
These results
cient
of methylenecyclooctatrienyl
with para-substituted
rent effect excited
currents
protons
and since
observed
derivatives
‘H M+iRand UV to test
cs7j.
12, a peripheral
It is concluded
is apparently
anti-aromatic
the first
properties.
has given an anion.
that
structure
perturbed 10 best
example of a perturbed
10 or
arorr.a:ic fits
annulenyl
the
an-
n-butyllithium
A novel
by ‘H NMRto involve spectra
were obtained
rearrangement
of 13 to 14 has been shown
the intermediacy
of carbanions
15 and 16 [48].
for
The latter
of 17 to 18. preparation
catalyzed
the corresponding represents
intermediates
a new and very convenient
of the 4,8-dihydrodibenzo[cd,gh]pentalene
sulfur-containing
10-a electron
for
the
15
18
17
16 Two cyclic
route
system.
14
13
Similar
in the conversion
anionic
systems have been studied
In the first
case,
19 gave 20, the ‘H NMRof which led the authors
to speculate
the presence
planar,
Secondly,
by NMRto determine
the extent
10 n-aromatic
delocalized
ture of 2i and 22 afforded is delocalized
into
of aromaticity. system [49].
23 whose ‘H and 13C HMRsuggest
the thiophene
ring of this
/\ 0 f3+3-CH3
molecule
0 -
of a mix-
that negative
charge
Li*
20
(WLH3)- Li+
a,,, 22
23
of
of a
[50].
0
19
21
metalation
metalation
i Evidence data for ides
has now been provided
the previously
(24)
and alkali
inferred
dipivaloylmethides
vided data as a function ample,
the greatest
lithium
cation
cation.
In
E.Z-
(26)
kali
cation
by ‘H NMR, far
ion-pair
[52,53]_
alkali
is lithium
sities
of the signals
cator”
in the titration
solvent.
and the E,Z-isomer from
shift
of the cation. was produced
was effected
pro-
For exby the
by the cesium
in methanol as a function
acetylacetonates
In this
cation
dibenzoylmeth-
Each of the techniques
‘H XHR has been employed to study the amounts of
papers,
(27)
[51]_
charge density
downfield
and conductance
of alkali
in the ‘H RNR spectra
shift
the smallest
tWo other
and Z.Z-
(25)
of the positive
downfield
while
infrared,
structures
both
chelation (26)
is unimportant
predominates.
conformations
have
of sodioacetylacetone
except
cji al-
when the
The integrated
inten-
been employed as an “indi-
with lithium
salts
H
H
H
24, R = Ph
26
27
[53].
25, R = I-C4Hg_ Radical
intermediates
dichloromethanes
(aryl
by ‘II and “F
studied
Such effects arylmethyl
in the reactions
chemically
were observed and butyl
of diarylchloromethanes
= phenyl and pentafiuorophenyl) induced
nuclear
on 28 and 29 arising
radicals
polarization from in-cage
and recombinations
and aryl-
with n-butyllithiun effects
were
[54]_
recombination
of arylmethyl
radicals.
of re-
spectively.
,!r(Cl)
tively
example of diastereotopic
charged
silyllithium
silicon
[55].
the nonequivalence of 185”_
A barrier
Metalation ‘H,
atom has been observed
of the diastereotopic
nega-
in the case of diisopropylphenylof this
comoound revealed
methyl groups even up to temperatures
about silicon
of two phosphonate
13C, and 31 P NMRspectroscopy
metalating I-butoxide
groups caused by a tricoordinate
Thus, the ‘H 270 MHz NMR spectra to inversion
I
Ar(C1) 29
28 The first
CHAr
ArCH-
AriHC4Hq Ar(C1)
esters to afford
of >24 kcal/mol
is suggested.
(30,
R = H or CH3) has been shown by eithe. r 31 or 32 depending upon the
Thus, while E-butyllithium affords only 31, lithiumagent [56]. and potassium t-butoxide gives both 31 and 32; the latter species
S
predominates
with potassium
cation_
CH3CH20,
CH3CH20 \ , CH3CH20
[
CH3CH2dp%-+C\.OCH 0
5-
CH3C”20’r2CH3 O-_iiO*
3
6
R 31
30
1
Finally,
H NMR, infrared,
33 and corresponding and the related tion
CH3CH20,
:I
q--iHC02CH3
sulfur
arsenic
of silylethers,
32
and Raman data have been published
and selenium
derivatives
phosphines,
derivatives,
and for
These species
[57].
for
lithium
alkoxide salt
were prepared
34
by reac-
and arsines.
H3SiOLi 34
33
tra of
were its
obtained
dianion
from
tetraphenylethytene Lipfield
[58].
Tines for
of the dianion
both the dilithio
ions are also
of alkali
of the metal,
and the cation
size,
the hv-
than is the latter
one.
gave
as only one other
midway
are rapidly
Ultraviolet
spectra
exchanged of the dian-
The authors
[SS].
between the contact
the
u-carbon
of the enolates
alkali
metal salts
of several
and others
chemical
with
enol
compared to the reference
density
at the a-carbon
shift
where shield-
of the ion pairs
[60]_
derived
and the
same carbon
ethers
shifts
as the
to be spread more evenly
the chemical
metal enolates the
the exis-
chemical
shifts
of lithium
is emphasized_
have been obtained
compared
and trimethylsilyl
charge
The danger of comparing
n-system.
atoms
the negative
discuss
ion alpha-carbon
dependency on these
causing
by ’ 3C NMRas a func-
has been studied
and temperature
the solvent
The 13C NMRspectra
r-electron
as well
salts
t%e lithium
and sodium cations
that cations
reactions.
diphenylmethanes
dependence
to those of other
acetates
is suggestive
solvent,
is decreased
cyclohexanones, late
both lithium salts
ppm for
compound confirms
in the order methyl-THFz-THFXiME, and solvation
temperature throughout
and disodio
ppm and 43.42
to the dianion
containing
and intramolecular
tence of a linear
salts
dilithio
such spec-
Thus,
reported.
Solvation
ing occurs
52.66
is closer
and disodio
betr-reen the above two lines by both inter-
and the
of
compared to the parent
that the former cation
That solutions
tion
shifts
respectively,
and sodium salts, pothesis
to ’ 3C IiMRof organ01 ithiums.
papers were devoted
Several
from acetophenone,
chemical
atoms
of
The difference
the
shift
of
in chemical
compounds seems to be related
and is a function
of
the
corresponding
the cation
enoenol
shift to the
(K*>Na+>Li+),
9
the
solvent
(DME>THF>etherf,
and added
Tigands
Tike
HYPA and certain
crown
ethers. A l3 C WR port
the
of
several
coupling
were found to be higher ascribed
coupling
-t-lithiosulfoxides
such carbanions
that
Thus, the 1J(13C-H)
[611fones sult
study
theory
is in the opposite
pounds methyllithium
and cethane
reagent
in radicals
butene
is discussed
not be understood radical
of
18-crown-6 ducts
ether
The authors
adequately
without
ketyl
of
thienyl
[65],
were also
sui-
with the model com-
constant
is
smaller
in the
1,3-carbon-carbon
interactions
cyclobutene,
that “spin
conclude
recognition
of
is not necessarily
these
on spin
and trans-2-
densities
simply can That
interactions.” than such anion
greater
soio
is discussed_ for
phenalene
35 [53],
phenyiazulene
2.2,6,6-tetrarzethy’cyclohexanone and thiazoyl
five
of phenylacetylene
troscopy
of
[62].
have been reported
various
and
sulfur compounds, a reThis increase in the
realized
the coupling
SUD-
position
lithiosulfoxides
state.
direction
uhere
the
in the parent
from benzocyclobutenes.
to 8-hydrogens
the lithium
ketyls
derived
hyperconjugation
ESR spectra [63],
of
does not
even in a benzylic
than in the hydrocarbon.
In the area of ESR, the effect density
:ransmissions
constants
than those
to a change in the hybridization
constant
organolithium
cation
and sulfones
are pyramidal
ketones
arylphospine
1673.
including
derivatives
In the latter
employed to demonstrate
[6a].
and alkali
infrared
36 rwtal
of dihenzo-
the affect
f66],
case,
alkali
metal ad-
and optical
spec-
the reduced nature of such species.
4 0
36
35 Spectroscopic
studies
to be investigated. rivatives
of
Thus.
nitromethane
using the
techniques
infrared
other
in the C-H stretching -1 are ascribed
m31- Bands at 3040 and 3170 an
with a sp2 hybridized carbon atom. The infrared spectra of several bonylates
were obtained
ment [69].
The data.
provided contact
information and solvent
to indicate in connection
than ::MR and ESR continue
and Raman spectra
alkali
region
of
alkali
metal derivatives
formulation of manganese caranion environ-
and conductivity
experiments,
about the nature of bonding and complexation separated
ion pairs
as well
as in
de-
have been investigated
to the aci-nitro
the nature of the carbonyl with kinetic
metal
free
ions
phenomena in of
several
10
study.* resolution
species.
In an unrelated
rections
of the transition
obtained
by the use of absorption
Ultraviolet
spectroscopy
brium constants lenide, anions
causing
by.the
an increase
The ion pair
and the di-
at 860-560
have been
nm [70].
and ESR have been employed to measure the equili-
tetracenide,
are favored
structure
lithiotetracyanoquinidometiiane
spectroscopy
of the disproportionation
anthracenide,
reactions
moments of
of vibronic
of the ion pairs
perylenide.
interaction
of
the cations
in the coulombic
propagation
with the aid of UV spectroscopy
actions
[72]_
Three types of anionic
Iithium
in ether
naphtha[71]_
The
with the resultinn
di-
energy.
in the polymerization
studied
of
and pyrenide
of
to check for centers
isoprene
in THF has been
the occurrence
are observed
of side-re-
at 287 MI, 305 nm,
and 335 run. two of which may be due to 37 and 38. Li+ -CH2-CH\~-+CR2 ZH3 38
37 in this
Other papers of interest arylthiolate
anions
the ion pairing (ethylene
using
alkali
visible
1751, and determination desorption
studied
mass spectrometry
with methyllithium values
l-727,
2.025;
C-H bond length
1.078.
1.0623
to 1.1185
(if said
tetrahedral
mostly
from the lithium bond is suggested
-46.9596, -46.4203.
calculated
to be -185.4886
to -185.8611
total -53.744
energies [78],
(8):
-39.318
The total
described
papers were employed,
2_021:1_q69. 104.2”;
to -39.401,
(Hb), total -46.419
Monomeric methyllithium
[79]. (&:
hartrees
of the C-Li barrier
[Sl].
species
Clusters
ranges
tetramer
Li-Li:2.369-2.68;
energy of this
is
transferred
Methyllithium
Li-Cr has been
containing
[Sl].
of methylenedilithium
-53.131
by
[76]_
(Ha) and 1.068 105A”,
and the inversion
as follows
[Sl].
spectra
sets
The bond separationenergy
upon bond angles
as having bond lengths
Similarly,
five
bonding with about 0.8 electrons [78]
[73],
of carbanions
attachment
1.090
of
of poly-
substances
reagents,
1.122,
planar),
kcal/mol
are also
cation
C-Li bond length
l-089,
C-H: 0.95-1.095
be (hartrees)
lithium
upon angle);&H:
2.25-2.31;
ten atoms of lithium
formation
Depending upon the basis
to the methyl [77]_ to be -5.6
spectroscopy
of non-volatile
-46.7767,
of ionic
ion pairing
and fluorescence
on organolithium
(ii):
(if
from O-4 to 20.31 depending is described
using
(depending
) , -46.247
to consist
weights
have been described:
energy (har Zrees) : -47.0206,
ion pair
[74].
[77-al].
the following
by optical
by absorption
of molecular
In the area of calculations concerned
a study of
metal compounds in the presence
spectra
of xanthene and thioxanthene field
include
in THF and DMFdetermined
of fluorenyl
oxide)
area
(cis,tetrahedral)
have been calculated [80],
-53.074
to
to -53.030
11 (trans.
planar)
[SO].
wise described 1.208 i;
C-H bond length:
charge distribution calculations, state
and -53-7165
by the following:
1.056 w [77].
in this
of 39 rather
are discussed
[SZ].
Lithioacetylene
Another paper discusses
than 40 [84].
including
A wide variety
I-fiuoro-i-lithiocyclopropane,
42. and others
Li C
C--
Li-CsC-Li
40
Using ST0/3S atomic (43)
of solvent
lithium
A calculated E86].
time scale, = solvent cussed. suggested C871-
computations
structures
l-l-di-
below [S’i].
H
soecies,
computations
of pentadienyllithium
a bridged
lithium
CT and C5 have previously structure
dimethyl In another that
were performed
on both the co-
[SS].
In an attempt were also
it is concluded to determine
oerformed
the
on all:Jl-
to two trater noiecules.
structure
this
42
of allyl!ithium
than 43 by 6 kcaI/moI.
which contains
Since
(44)
on this
coordinated
proposed
41 and its described
41
orbitals,
and ion pair
that 44 is more stable affect
ethyl-
1-3-dilithiooro-
H Li
39
valent
orqano-
[77],
6, + 1; --;---(
Li
usino ground
of other
and vinyllitilium
and LiCH2X where X = LSeH, XH2, OH, F, and 9H2 1781, pane, difluorodilithiomethane. tri- and tetralithiomethane. salt,
the electronic
bridged
lithium
lithio
like-
paper or-edicts,
has a’double
ethyllithium
is
1.931 .t; C-C bond length:
compound 1833 Nhile a third
that monomeric dilithioacetylene
structure
lithiums
to -53_7851
C-Li bond length:
ether.
is said
the lithium
interacting
ether)
by both :-
has been
and z- bonds
been shown to be equivalent
to be equilibrating
The affect
paper dealing
bis(dimethy1
on the F!YR
as shown (45)
where 5
of methyl groups on such anions
with cyclopentadien:rllithium,
atom is most stable
it
is dis-
has been
above the middle of-Ehe
rino
12
Other ring [80.88],
clopropenyl tion
systems similarly
anions
[go],
anions
aromatic
and antiaromatic
dianions
[88].
Two papers discussed Both agree
the orbital
containing
stable
have included cyclopropane
4-,
‘;-,
certain
b-,
7-,
of 3-oxypair
atom rather
[91],
[89],
reac-
anions
and 1-thiocarbanions
are stabilized
[92.
bonding.
Such sta-
is conformationally
than conformer
dependent where conformer 46 ( w or e) is more are oroSimilar nc-siH overlap integrals 47 (y or a)_ It is suggested
the C-H bond antiperiplanar
to the lone pair of electrons
is much less
acidic
than that
in its
H. “<-.
that
precursors.
on the -:t-heteroaton,
H H
/
C
in such carbanion
gauche rotarner.
H
d_.
Q Y X
‘.
\‘C
;
B
46
\
47
ii
An -ab initio study has been performed on nitromethane. its aci-nitro and its conjugate base 49 [94]. The anion is best described
tomer [48],
but has an extremely
The total parent:
and
by overlap of and a .G* anti-
of the carbanion
than by (d - p),
posed for e-oxycarbanions_
planar
cy-
and other
and g-membered ring
alpha to sulfur
the lone electron
on the sulfur
anion
the electrocyclic
ant! butadiene
8-,
aspects
lithiocyclopropane
radical
[80],
of cyclobutene
that carbanions
bonding orbital bilization
[80],
3,3-dilithiocyclopropene
between the radical
931.
studied
I-l-dilithiocyclopropane
energies -243.2630;
CH2=rI
shallow
(hartrees)
for
48: -243.2532;
potential
49:
to pyramidal
using an extended
inversion_
basis
set are
-242.6573. 0
r”
-
H.$..
\ OH
+// \
o-
H#=N
a 0-
48
+i’ I
0
_
49
Other Papers discussing
mdlecular
with the SRy 1 mechanism of aromatic anomethide’C961,
curve
the species
tauas
and the structure
orbital
calculations
substitution
of the lithium
[95],
have been concerned
the structure
of tricy-
adduct of nethylenephospho-
rane [97]_ 3_
KINETICS AMI MECHANISM Several
to test cesses
if
:ypeS of ketones have been condensed with lithium dimethylcuprate the nature of the products could determine if electron transfer pro-
had occurred
to afford
radical
anion
intermediates
C98.991.
Thus, aryl
13
alkyl
ketones
tions.
50 with this
Though ketyls
detected_
Similar
attack
than to an electron was observed of
cuprate
products
transfer
process.
no products
ketyls
arising
from 51 were
of certain
ketones
52 gave
on the cyclopropyl
On t.he other
ketone 57.
diary1
ring
transfer
54 to ketone 55 and
In another
ketones
were rather
hand, such electron
and bromoketones
enone 56 to E.-f-unsaturated
affords
from 1.2-addi-
53; horrever, such products
reagent
of acetoxy-
that the reaction
arising
with cyclopropyl like
by the copper
in the conversion
Z-cyclopropyl
is disclosed
of the cuprate
ring-opened
to direct
gave methyl carbinols
may have been present,
reaction
some of the desired ascribed
cuprate
paper.
with lithium
it
dirrethvl-
[loo].
0
R’
53
52
51
50
R
0
R
0
0-
I
54 The electron been studied [lOi]_
transfer
as a function
efficiency
of g-methoxyfluorenide
in methanol has
of the nature and concentration
It was found that the second-order
irreversible
57
56
55
nitrobenzene-oxygen
trapping
rate
of
constanis
efficiency
the counterions
for
ionization
are in the order
and for (CH314N*
~l~~Y,OCH3~~ilaOCil3--LiOC~3_ Benzhydryl by lithium
results
These
chlorides radical rate
are conirasted
to similar Similar
in the reactions
mass spectrometer
and absolute
gas phase acidities
Such acidities
transfer
reactions
mechanism [102]_
of corresponding
mechanism through a geminate
mechanisms are suggested of diphenylmethyllithium
is of
is discussed.
rates
of a variety by pulsed
The relative
of several
since
to explain
the
with benzylic
of
anions
resonance
acids
[103]. of sol-
the measurement of oroton-
with related
spectroscopy
58 and 59 towards
why desired
electron relative
and the importance
Another paper describes
to determine
in a pulsed it discloses
carbon and nitrogen
acidities,
of delocalized
ion cyclotron
reactivities
in an effort
generated
interest
are compared to solution
energies
as determined studied
coupling
gas phase carbanions
hioh-pressure
transfer
to ethane derivatives
displacement
and chlorides.
A paper describing
vation
have been dimerized by a classical
via an electron
intermediate_
differences
fluorides
apparently
which occur pair
fluorides
and benzyl
naphthslene
alkyl
neutral
halides
ranoalkylations
species
[104]. have been
of species
like
14 58 afford
of mono- and dialkylated
mixtures
that such carbene
anions
of the more substituted
suffer
products
dialkylation
The authors
[1051. of
because
the greater
conclude
reactivity
anion.
58, R = H 59. R = CH3 The equilibrium lithium
anionic
polymerization
of n_-valeraldehyde
benzophenone has been investigated
of -5.3-0.3
kcal/mole
and -25.7r1.4
cal/mol-deg,
effected
by
Enthalpy and entropy
[106].
respectively,
values
have been dis-
closed. Equilibrium ters
solution
acidities
of a number of phosphinylacetic
in diglyme and in DMSOhave been disclosed
it has now been established are observed tions
that kinetic
not only with different
The kinetics
of the disproportionation
of the alkali
illustrates dianion
cation
salts
by fluorene solvents protonated
ion pair
is protonated tight
tTll]_
tetracenide
four-five
The kinetics
alkali
ca-
The study
radical
anions.
orders
of
species
faster
than the cor-
fluorenyllithium
the former system reacted
and solvent
has been
separated two-three
ion times
one_ of alkali
derivatives
of the cation,
to the tightness
with the potassium
of ethyl
the solvent,
of ion pairs
[112-J.
than with the lithium
of the solvents
acetoace-
and the alkyThus, more salt
and in
are deemed more important
than
constants_
Other kinetic
studies
and lithium and styrene
have been performed [113],
n=butyllithium
on the systems bromobenzene, and 4-methylmercaptoaceto-
and lithiumdiethylamide[115].
in the area of stereochemistry,
the Z/E equilibrium
is
and that the sodium
of magnitude stuay.
of ethereal
the lithium
ion pair.
carbanions
and sodium
in a variety
ion oair
an-
for certain
1,3-diphenylallyllithiun
revealed
RWA than DMF- The ionicities
phenone [114],
corresponding
of
In another
of 0- to C-alkylation
dielectric
radical
as a func-
[109].
free
than the latter
is realized
photolysis
favoring
agent and is ascribed
benzaldehyde,
flash
than the tight
has been found to be a function
0-alkylation their
of alkali
spectrophotometrically
ion pair.
under conditions
The ratio lating
Hith different
it was found that the loose
lithium
more rapidly tate
but also
ones may be responsible
than their
the protonation
about 100 times faster
responding pairs
of C-H acids
have been determined
using
than steric
have been determined
[llO]_
alkylated
other
being more stable for
dianion
and solvent
that factors
Rate constants
tight
effects
espaper.
[lOS]_
ions to the parent compound and its tion
differentiating
anions
acid
In an unrelated
[107].
compositions
of
15 several
E-alkenyl
been studied the Z/E ratio endo (cis)
organometallics
as a function increased
preference
60 (R = CH3. CH3CH2, i-C3H7. f-C4H9)
of cation,
in the order
R, and solvent
[116]_
Li
between R and the alkalimethyl
pendent on the electronic
capacity
or the size
carbon
of R.
have
It was found that Moreover,
the
seemed not very de-
Reasons are suggested
for
the above observations. RCH = CHCH2M 60 3-#ethyl-Z-pentenyllithium hydes , acetophenone,
mounts of branched factors
[117]_
p-electron
has been condensed
acetone, (61)
and linear
The ratio
withdrawing
alcohols
of 61/62
groups_
ing groups _ Only 61 and only The results
respectively.
with a variety
and hesafluoroacetone (62)
decreases
a-
electronic
with o-electron
VJith acetone
in terns
of
of benzaldehydes
is realized
62 are obtained
are interpreted
as a function
in reactions
The opposite
of benzalde-
to study the relative
with donat-
and hexafluoroacetone.
of hard-soft
acid-base
theorv. OH
OH
/+AR
-_-
-_.. >
i 62
61 The effect
of
has been studied higher cifically
alkali
metals
with methyl
gave nearly alized
ion pair [llS]. iodide
a SO-50 mixture
in terms of a cation
63
siructures
in THF by varying
on the methylation
the cation
Thus, while to afford of mesoside
the lithium
meso-
of nethyl
64
salt
(:- 99:),
and racenic-64.
approach
stereochemistry
systematically
from lithium 63 reacted
iodide
63
are ration-
to diastereomer
65
to the
stereosae-
the rubidium salt The results
of 63
65.
16
i4etalation
to afford
of
(+)-(S)-3-methyl-Z-pentanone
(S)-enolate
has been reacted give optically
67 with less
with alkylhalides. active
hy LI\IP&has been show
(66)
than 10% racemization acid
chlorides,
Reagent 67 and ketones
to
products _
0
Oti
67
66 In the continuation of addition
[119].
aldehydes,
reactions
of an earlier to carbonyls
study concerned
with the stereochemistry
in terms of orbital
factors,
the relative
amounts of 68 and 69 from 4-t-butylcyclohexanone with MCH2Y\-rere found to vary Thus, less 69 was obtained with LiCH2Y than with the metallic cation [120]. with BrZnCH2Ywhere Y = C02C2HS. CONR2, CIi. and CO2M.
69
68 Several afford
ester
the 1,2-adducts
terestingly, ing,
lithium
the thermodynamically condensation
have been*condensed
70 at -7g0 by a kinetically
when the reaction
a similar fordino
enolatrs
mixtures
controlled
are allowed 1,4-adducts
with a lithioacetonide
with 2-cyclohexenone
controlled
process
to
[121].
In-
to warm to 25” before quenchIn one case, 71 are obtained.
was found to.be
irreversible
af-
only a 1,2-adduct.
LiO
t;i
+
CH3$Cfl$H3 X
The intermediate lithium
-7 71
(X = CH3.0Ph.OCH3.SPh.SCH3)
70
dimethylcuprate
ium enola:e
organometallic
to enone 72 has been found to consist
73 and insoluble
troscopy
[122].
probably
intermediates
obtained
from the conjugate
(CH3Cu), precipitate
It is suggested in all
even when the organocopper
that
lithium
such conjugate
product
as evidenced
rather additions
remains in solution.
X C02CH3 addition
of
of soluble lithby 13C RMRspec-
than copper of lithium
enolates cuprates
are
li
OLi
0 ether
(CH3)2CuLi
73 Other sutudies (S)-lithiobenzyl acid
[123],
in this
the stereochemistry
dihydroanthracenes valent
[124],
phosphorus
nethoxide
to afford of
the silylation
and the inversion
atoms of two phosphinate
with the carbonation
of
(R)-:i-nethylsulphinylphenylacetic of 9-alkyl-lo-lithio-9,lo-
of configuration esters
at the chiral
by methyilithium
tri-
and sodium
[125].
Several 1976.
area have been concerned
methyl sulfoxide
papers describing
A continuation
has resulted
in the discovery
control
[126].
erythro
acid
For example, enolates
has also
of organolitiiums
of the ester
enolate
of solvent
that choice lithio-(E)-crotyl
75 in TtiF and to threo acid
Z- and E-type
reaction
rearrangements
of the study
appeared
Claisen
dictates
propanoate
in
rearrangement
stereochemical
(74)
rearranges
to
76 in THF-HHPA. It is suggested
This
are formed in THF and in THF-HHPA, respectively.
been employed in the construction
of the prostanoid
[127]. H
H
that
skeleton
-
CH3
” vCH3
.-
OH ti
of alkali
The isomerization all
for
cis
77
_‘._ _:
and potassium
cations,
been effected
by protons
anion 77 to the
a much higher
where the &Gf of the isomerization
lithium
of 77 to 78 has also
.;
cis,cis,cis.trans-[gjannulene
78 has been found to require
than topomerization kcal/mol
76
74
75
more stable
OHH
0
CH 3
respectively
activation
energv
ranged from 29.6-34.3 Isomerization [128]_
and by photochemical
78
and thermal
16
A fuT1 paper appeared describing
with cholesteryl ring
systems participate
found for result,
Several
ring
salts
the Stevens rearrangement ethyl,
tosvlate.
reactions
were
As a
which occur
sp3- carbon atom_
of methallyamines
have been subjected
to
to 82 and 83, respectively_ %th larger alonly 82 arisinq from 80 was ohserved.
81
80
i
R-R’
R’
83
82
86 [131].
results
and cyclohexyl,
R /J ’
Quaternary salts
Similar
and other bases [130]. When R and the reaction proceeded via a mirand n-butyl.
79
bases to afford
dialkylcuprates
by n-butyllithium
n-propyl,
i-propyl
lithium
[129]:
in these
at the nucleofugal (79)
ture of 80 and 81 which rearranged kyl groups like
reactions
are observed
of configuration
of
in which the double bond of the
of cyclopropylmethylcarbinyl
reorganizations
quaternary
R’ .were methyl,
tosylates
in substitution
the cycTopropane
skeletal
with retention
the interaction
and 5-norbornen-Z-y1
84 (X = Cl,I)
Stevens rearranged
The amines arose
were also product
treated
from a cormnon intermediate
a5
with a variety
85 and Sommelet rearranged
a6
87.
87
of strong product
19
Similar
have been observed
rearrangements
amines 33 and benzyne.
generated
[1323.
Among the products
induced
by excess
in the reactions
from o-fluorobromobenzene
observed
of silyletkyl-
and n-butyllithium
The cyclization
were 89-91.
to give
90 was
n-butyllithion. :*3
Certain sulfones step
like
h-arylbenzenesulfonamides 93 upon treatment
in such reactions
fonyl
like
92 have been found to rearranqe
with organolitkiuo
is metalation
91
90
89
88
of a ring
reagents
[133].
to
The first
hydrogen atom ortko
to the sul-
group.
93
92
The previously
reported
found to be reversible lithium
counter
[134].
rearrangement
stabilities
Na
I
I
Pk C-R 2
N-Ph I
to 94 by tke use of
of sodio-95
c0zc2*5 Ph2‘,
of 94 to 95 has now been
Thus, 95 may be converted
The relative
ion.
discussed.
1,2-anionic
,’ \
versus
lithio-94
are
C02C2H5
-Ph
Li
95
94
Ketazines their
have been converted
Jilithio
is determined
salts
as illustrated
to pyrroles
or tetrahydropyridazines
in Scheme I [135]_
Which nroduct
via is formed
by the nature of the R and Ar groups.
R mechanism has now been proposed for the conversion of 96 to 97 involving, lithioaziridine 98 which has been trapped among other proposed intermediates, with methanol-O-d
[136].
0
0
P
NH-c-C6Hll
I c-C& 96
1
Ph 97
I c-C6Hl 1 98
20
Scheme 1
Ar
I
Products from
the
99-101
tiittig
(R = 5-hexenyl
rearrangement
by n-butyl-
and methyllithium
group
via
arise
of
pathways
secondary recombination of alkyl to 99-101
which
contain
the
orcyclopentylmethyl) benzhydryl
[137].
intramolecu’lar
2.2-3.0 LDIpA THF
radical
Ghexenyl
have ether
in
been obtained THF effected
Those products containing the 5-hexenyl which
may involve
and ketyl.
cyclopentylmethyl
group
routes
other
The cyclizations are
said
to
occur
than leading with
5-
21 hexenyl
radicals
which escape
with appropriate
reaction
with geminate
partners
but later
react
ketyls. R
!
; &
Ph2C-OH
.cFL/
*6&.Ph P”.
_. -’
( Ph 99 Two papers discussed siloxybenzenes. lustrated
and other
pyridines.
by the conversion
some cases,
of
fail
[lSO].
a portion
the synthesis
rides
4.
of
substitutioh
in contrast,
il-
route
in
1 ithio-‘J-
of the first
in the reactions
have been concerned
with the con-
rearrangement cyclophane
of a dithiacyclophane
within
a cyclophane
as
[ICl],
and
of tributylstannyllithiun
with aromatic
fluo-
have been metalated
by n-butyllithium/T!-?EDA
c142].
METALATIOZS A.
At so3 Carbon Several
polymethylbenzenes
in hexane to afford tion
The process,
to (El-2,2-diphenyl-l-methylthiovinyl-
the us;? of the Vittig
and chlorides
in others.
rearrangements
of 5,5-diphenyl-4-thiacyclohexene
cyclopropane tine
route
[139,139]_
by an intramolecular
to undergo such rearrangenents-
Other papers discussing version
heterocyclics
102 to 103, occurs
but by an intermolecular
iriaiky1silylarylaaines
101 in lithio-O-trialkyl-
100 anioni c 0 to C rearrangements
[143].
clusively
di- , and trilfthio
mono-,
For example.
mesitylene
The energies
105.
and are included
derivatives
gave mostly
of these and related
104 while species
as evidenced p-xylene
by silyla-
yielded
ex-
have been calculated
in the paper. CHLi2
CtQLi
2Li+ LiH2C fiCH.$_i
@ CH3
104
105
106
33
Four methallybenzenes above reagent
to afford
and isobutene
corresponding That dilithio
by methyl bromide [144]_ :!HR spectroscopy.
The methylated
enes were obtained
in preference
discuss
at great
methane dianion Metalation lithium
the
species
at a benzylic formally
carbon
delocalized
was confirmed
from cross
from linear
of the aromaticity
by dimetalation
of
by the
which were methylated
were present arising
to those arising
question
obtained
metalated
derivatives
derivatives
of 1.2-dihydropyrazines
occurs
tem containing yields
length (106)
have been similarly
dilithio
conjugated
ones.
by di-
The authors
of the trimethylene-
isobutene.
107 (R = Ph or p-ClC6HS) with n-butylto give
bicyclic
Sn-electrons
108 rather
[14S]_
than 109, a sys-
Hydrolysis
of
108 then
110.
108
107 A combination
of metalation-metal
lithium-potassium ene(lll)
t-pentoxide
to dianion
112, a very stable
ple cycloheptatriene cloheptatrienyl
hydride
[146].
elimination
reactions
has been emp!oyed to convert species
Oeuteration
of
by n-hutvl-
l-methylcyclohept-?-
which does not behave as a sin-
112 affords
the known methylenecv-
anion 113.
111 !*letalation
of
112
squalene
113
by s-butyllithium/TMEOA
has been found to occur
only
on a methyl group [147]_ prenylamine
In another paper. metalation of a methyl qroup of 114 by n-butyllithium results in an interesting isorrerization and
elimination
to give
isoprene
[148].
Other related
examples are listed.
114 Polymetalation tion yield
of acetylenes
continued
of 1- and E-butyne and 3-methylbutyne CH3C3Li3 and (CH3)2C3Li2,
densed with a variety
respectively
of electrophiles
to be studied
in 1976.
with alkyllithiums [149].
to usually
Thus, reac-
has been shown to
Such species have been conafford polysubstituted acety-
23
lenes of
and allenes
like
are best
described
sequential
soft
scribes
of
[lSOj_
The results
and acetylide
A second paper in this
are ascribed
sites
allenynes
C3Li4 gives
mostly
to proparqylic
sites
and reactions
and diethyl
C-CCC-Si(CH
)
(f!J3)p
(CSIj3
120-122
lithi?;n
C2%\ .=C=c~C2ii5 /‘Si(Ck!3)3
Zhile
[152j.
r20 and 122 were netalated
to afford
The authors
suggest
by n-butyliithiun
which have been condensed
121 gave a mixture
respectively.
by n-buty’llithium
have been mecalated
reagents
120 Regioselective dimetalations (123)
124 after
122 with chloroirimethylsi-
,Si(CH313
(CH3)3Si ‘C=C=C / &J ) .. ‘2 4
(CH2.i4
CH2-C-C
/
124
123 Seven I-arylpropynes order
rea-
on 1,Scyclotetradecadiyne
quenching
i CH2CXCH2
and trilithiated
of
only at the methyl and
that both netarations occur .ztthe same car-
CH2CXCH2 ‘.\ / (c\H2)3 (CH2)3
Pseudo-first
to
with a variety
of .I- and -:‘-nonolithium
121 have been e ffected
bon atom.
di-,
of which gives
113
proparqylic
lane El53].
being
paper de-
117
33
Cyciopropylacetylenes
carbon,
sulfate
A third
(C,E,),C-XX--Si(C1!3)3
L
118
electrophiles
and chloro-
[llj].
AE
Si
i-ring
hard.
116
2 5’2,
discussed
sulfate
of CH3C5Li3, derivatization
(CH3:2C=C=C,r
115
yield
series
species
117 alonq with some 118
being
and some cumulenes and diacetylenes
i
containing
by diethyl
and chlorotrimethylsilane
!CH3)2;4:c-E
(C 2.1
of which depends upon the size
the above lithium
these organometallics
For example,
the preparation
mostly
ratio
the
as proparqylides.
derivatization
trinethylsilarie and 119.
115 and 116,
An IR study suggests
the electrophile.
containing
various
ring
substituents
on the methyl group as evidenced rate constants
for
have been mono-,
by silylation
the monometalations
[154j.
were calculated-
24
Several
methyl ketones
have been regiospecifically
methyl carbon atoms with aldehydes 126
rl55-j.
by bulky
The success
bases
like
127 in the presence
enolates
that o-methyl-hydroqens
in preference
to p-methyl-hydrogens,
fects.
An additional
-c-hydrogen may also
of an acetylene
lithium
in hexane to give
ionized
via eliminaiion
probably be abstracted
of lithium
trilithio
too weakly
and o-hydroqens leading
ef-
to the foma-
salts
the conversion
131 by LDIPA in THF [158].
using alkali
metal
amides
failed
of triketones
Previous because
attempts these
like
130
to pre-
reagents
are
basic.
A similar
lithium
cyclohexyisopropylamide,
was found necessary
to
of 132 [159].
Lithium enolates fragment as indicated Glycidic
methoxymethyl
132
131
base,
ionization
134 [160].
are
of chelation
129
131)
effect
128
,CH2Li
paper has appeared describing
pare such trianions
like
oxide.
128 to their
SiZ
have been
species
because
,CH3
A full
[156]. .x \ Si
127
by n-butyllithium/TKDA It was established
and 129 [157].
Similar
co-reagent.
from esters
0
ring mono- and trimethylacetophenone
metalated
of 125 to
the metalations
126
125
tion
the aldehyde
OH
Several
td effecting
E-hydroxyesters
n
further
of
on their
by the conversion
of the method is ascribed
have been employed to prepare
bases
as illustrated
condensed
esters.
from methoxyirethyl
esters
at 25” and recombine esters
may be prepared
like
to afford similarly
133, though stable
at -79”.
hydracrylic
like
esters
by metalation
of s-bromo-
Lit
0 /CH20r-i II -- R2C=C=Of H-C-H + LiOCH3 - R2C
3: R2C_E&CH2&-CH3
\
+LiOCH3
133 Lithio-t-butyl talation
of
dehydes
to give
pared simi?arly, [162].
silylester
acceotors.
reacts
(135)
esters
[161]_
Lithio-t-Duty7
with aldehydes
have been (1361,
-:,:-unsaturated
prees-
-_si __-’
ester
enolates
of undergoir;g are
generated
like
thio
by LDIPA at
as Part of
I! R’CHpt 139
to be metalated
organolithiums
to afford
have been
0
138
the resulting
ester
(1381
139 [163].
[164].
As fLi continue
like
with formaldehyde
0
esters
and ketones
esters
the parent
been condensed
137 thio
[166].
of
thiol
of u-methylerie-y-thiobutyrolacione
i CH2=CSR
For example,
to afford
by metalation
OLi
Certain
137 and ,-thiolbutyrolactone
al kylation
136 has also
Lichiolactone
the preparation
alpha
io sulfur
by LDIPA.
140 and 141 have been condensed with
a,?-unsaturated
esters
[165]
and chiral
thi-
respectively.
S(O)
S I!
Li
LiCH2-SX-OR
RO:, , CHC02C2.H5 S
141
140 A variety of
al-
ii
thio
The enolates
tions
of
tl
Lithium
metalated
by me-
a variety
esters
to yield
Li
found capable
iranes
The latter
and ketones
!
aldehydes
with
trimethylsilylacetate
(ESi)2
-73”.
-
has been obtained
by LDIPA and condensed
vinyl
a-silylated
shown to be Michael ters
134
bis(trimethylsilyl)acetate
the parent
co2cc;3
of phosphate
by n-butyllithium 143 with aldehydes
esters to give yields
0
I! _
R2C=;-CH20P(OC2H5)2 R
142
and phosphoramides intermediates
like
like
142 have been di-
143 [167]_
lactones.
.+ 0
‘I’
R2C-7Tq
II (OC2H5) 2
R 0-Lf+ 143
Condensa-
Interaction of N,IJ-dimethylbenzamidewith LiTMP to afford 144 proceeds via The latter organolithium reagent may arise the dipole stabilized 145 [168]. from metalation
of the methyl group syn to the carbonyl a related carbanions are described,
oxygen. reaction
examples of similar ethylbenzamide
results
tional
In a different
group_
mide by s-butyllithium more stable
only
in ring metalation ortho to the carboxanide funcof !1,M-dimethylthiopivalapaper, the metalation
to afford
146 is discussed
than 145 is evidenced
with alkyl
halides,
nucleophilic
aldehydes,
by its
ketones,
aninoalkylation_
[169].
That 146 is apparently
sufficient-life-tine to be condensed Such condensations represent and OHF.
_
146
145 Hippuric
has been converted to its
acid
and then al kylated
to give
similarly
and condensed !_i
prepared 0
148 [1703.
trilithio
Dilithio
salt
salts
with alkyl halides !
YH.I_.
147
Li
of 151 with LOLPA has yielded
yields.
nuder
of alkylating
Similar
as part of the synthesis
i
metalation
/R
;
\-
like
Subsequent
gave d,S-unsaturated
of acrolein
of species
150
152 [172].
agents
OSiZ
OSiE R
Oh
0
of 152 with a large ployed
,/ 0
148
149
in excellent
F
Li
ii lletalation
147 by LDIPA/TMEDA
149 and 150 have been [170,171].
Ph/9
0
Though other on II,N-di-
cyanohydrin
153 11731.
reaction ketones
has been em-
m-Tolunitrile ford
has been metalated
154 [174]_
Condensations
In a different reacted ducts
study,
with various arising
for
the first
with ketones
the three
isomeric
time using LDIPA to af-
and alkyl
halides
are described.
bis(cyanomethyl)benzenes
amounts of methyl1 ithiu ii: and methyl iodide
from multinethylation CR
[175].
155 have been to give
pro-
CIi,CN L
0 a L:
CH2CN
\.
154 papers disclosed
Several with bases
additional
such as LDIFA, lithium/diethylamine
ethylamide.
Such netalated
amines like
kyl halides
[176],
:l-bromoacetals
haloalkenes
[179].
epoxides
imine has also
been cetalated
ot- ii-alkylated
as a function
!177],
dihaloalkanes
and chlorotrinethylsilane
the cation
156
imines
156 and 137 have been alkylated
by netbyllithium of
of
in benzene/RMPA, and lithium
and ketals
[180].
155 of the metalation
exa::ples
to give
[178],
[lSl].
di-
by aldi-
A bis-
158 which has been C-
and solvent
[182].
N
157
Ph 158
In the area of oximes,
the position
Governed by the configuration and condensations
with aldehydes
Thus 159 and 160 afford cyclic
ketones
iodide
occurred
lithio
oximes have also
azoles
[187]
Several after
like
oxines
and their
the axially
[183]
also
work up. hydroxylamines
has been shown to be
and ketones
and by deuteration
[184]_
product
al kylation
[185,186]_
chlorides
to qive
P-isoxazolines
of organolithiums
4-acylisox[ls8]. to afford.
_ Lit R
HO,
160
161
162
by methy
Such di-
163 [189]. Li+
159
alkylation
In the case of oximes from
to yield
underwent addition like
by subsequent
O-methyl ethers,
substituted
been condensed with aroyl
and with aldehydes
lithiated
and ketones
161 and 162. respectively.
cyclohexanone
to give
of -;-netalation
of the oxime as evidenced
163
28
A large
number of N-N-dimethylhydrazones
tones have been regiospecifically
[190,191,192]
ety of electrophiles aldehydes
[191],
to afford
polyfunctional
The use of chiral
chiral
ketones
enolizable.aldehydes
by LDIPA
to give
a;ld ke-
derivatives
[190,193],
v-hydroxycarbonyl.
compounds [192],
165 in alkylation
1,4-
164
with a vari-
aif!-unsaturated
and l,S-dicarbonyl
and a-thiomethyl
reactions
like
species
164 and 165 have been reacted
alkylated
6-hydroxycarbonyl.
compounds, other c1943.
metalated
Reagents
and 165 [193].
of
gave,
after
compounds hydrolysis,
[193].
(CH3)$\ N Li * ,C
‘c
/
iin 165
164 Several
other
phenylhydrazones,
zones have similarly certain All
hydrazones
of these
sis,
tions
168 affords
alkyl
active
halides
ketones
enamines from certain
n-butyllithium
species
to give
trilithio
[199].
chiral
166 [195.196]
reagents
[198]_
sulfate
In a different
indanones
The results
lithioenamine
and dimethyl
like
while
167 [I??].
169 which has been to give,
paper,
and a cyclopentenone
obtained
from subsequent
after
hydroly-
metalation
of pyr-
were effected methylation
by
reac-
are presented.
169
168 Allyloxy lyl
and N-p-tosylhydra-
like
have been condensed with electrophiles. Li
of chiral
by several
optically
rolidine
to dilithio
have been metalated
reagents
Metalation alkyiated
N-benzoylhydrazones.
been converted
ethers
with aldehydes Internal or chloro
carbanions
like
by s-butyllithium and cyclic
cyclization
172, condensations
ketones
reactions
substituents
170 continued [200,201,202].
[201].
to be prepared Condensation
gave mostly a-type
by metalation of
products
of 170 have been observed
of al-
170 (R = Si(CH3)3) like
171 [200]_
when R contains
epoxy
In the case of the related pentadienyl lithium with a variety of electrophiles usually afforded mostly
29
y-substituted
products
like
173 [ZOZ]. Li+ .++
+,
Li
OSiR3
OR
Metalation
of propargylic
banion which reacts Hydrolysis
of
& P
174
Certain
acetal
with alkylating
the resulting
as if
illustrated
z,fi-unsaturated
Phi-‘-\e
derivatives
of D-arabinose of
a car-
175 [203]. esters.
175 and D-fruciose
to cause the elimination
by the conversion
gives
it were exclusively
yields
q/-
with n-butyllithium
The process,
174 by n-butyllithium/TYEO4 agents
ketone acetals
0-isopropylidene
‘been reacted
173
172
171
170
of acetone
176 to 177, apparently
have [204]. involves
ring metalaiion.
?H
HOCH2$H-CH=CH-C(C,H9)2 OH 177 Lithiation Phinyl,
of
178 and phenylated
PhenYlsulfonyl,
derivatives
1.2-epoxyalkyllithium
rea9ents
densed with
of electrophiles-
a variety
where R is a silyl,
and cyano stereospecifically
ethoxycarbonyl,
Such reagents
179 ~205.206].
phosaffords
have been con-
178 Choice of lithium gives
of solvent diethylamide
has been found to be very important in the interaction For example, 180 epoxides [207]. with -.,,S-unsaturated
181 and 182 in ether
182
181
180 Q-Ketosulfone
and HYPA, respectively.
183 has been converted
by LDIPA, then alkylated
to its
by 1,3_dibromopropane
corresponding
[208].
diiithio
salt
Subsequent cyclizations
30
via either
C- or O-alkylation
similarly
been prepared
then condensed with cyclopentanone
acids,
Dilithio
are described.
from the corresponding
salts
sulfinyl-
to afford
-f-lactones
Other sulfur-containing
organolithitun
reagents
prepared
the parent compounds have been 186 used in the synthesis 187 used to prepare monothioglycols
[Zll],
PhS or Ph2P0 used in the synthesis
[209]_
185
184
183
Z=
184 and 185 have
and sulfonylpropionic
and acyl
of certain
by metalation
of pillarose
anion equivalent
ketones
12121.
FI &H2Li
CY ‘\
Lid A full has appeared
L-2131.
SCH., J
187 the preparation
186 paper describing
189. prepared
Species
butyllithium. was condensed useful reactions_
with a variety
by metalation
Hydroxytin taining
reagent
190 with n-
in synthetically 0
been converted with alkyl
193 [214].
of a-vinylbenzyl
189
190
by reactions
compounds to afford
the conversion
anion
Ph3P a
191 has possibly
as evidenced
of ylide
+
189
butyllithium
Li
of ylide
of electrophiles
Li
188 u&-e
188
and reactions
0 Ph3i&
of
[ZlO],
A full
alcohol
to dianion
halides
192 by n-
and carbonyl-con-
paper appeared which discussed
to a dilithio
salt
[215].
OH
H--c H
Sn(n-C4Hg)3
H
191 A variety afford
species
trophiles
i
H_ 192
of nitroalkanes like
to give
194 [216]. 195.
193
have been doubly metalated Such reagents
by n-butyllithium
were condensed
to
at carbon with elec-
31
R-CH-X02 ; 195
194
Finally,
organolithiun
reagent
196, prepared
equivalent
derivatives
number of
to give
Organolithiuns
similarly
obtained
j
:,, R
-.
aryl)
\
Li-
Compounds like
R
by t-butyllithium
[221].
202 was demonstrated
netalation
In another
of ene-sulfides
ated faster
study
versus
than the latter
predominated
290
That such reactions
to sulfur
203.
0
which contain
talation
to afford
ones [222].
Vinyl
occurred
by condensations
involvinq
ene-ethers,
both alkyl the site
a comparison
me-
regiospecificalwith electroof the rates
of
rather
than ally1
metalation
with such ene-sulfides. E
203
202
201 In contrast hydrazones like
1
RSC=CHOC2HS
RS;=CHOC2HS
RSCfi=CH0C2HS
to References 190-194. interaction of branched :1&dimethyl204 with lithium in diethylanine/benzene/HMPA affords nitriles
presumably via vinyllithium densations
(or aryl)
of vinylic
the former compounds were metal-
Li
eliminations
like were
Li -i
,R
to determine
ly alpha philes
and 2110 [220]
199
have been studied
to give
afforded
species
?!\_/4
3.’
201 (R = Ph, n-CSHl,)
groups
to yield
forma-
and ketones_
I’ ‘,
198
and alkoxy
Com-
of a large
with LDIPA at -100”
of electrophiles
with aldehydes
atom of
Thus, treatment
0
2’
197
thio
the sp2-hydrogen
carbanions.
5
I! \l/
E-
[217].
carbanion.
199 (R = C1f20CH3and CR3) [219]
and reacted
5
Li-'
of
(R and R’ = alkyl,
197 which was condensed with a variety 193 CZlR].
to a formyl
rretalation
unmasked acyl
formar;ides
of the parent
to aldehydes
XITROGE:i
Three papers described nide
by netalation
ihen oxidized
compound by LDIPA, has been alkylated pound 196 is thus synthetically E_ AT so2 C4RBO;lAXD AT
196
reagent
with a-hydrogen5 with alkyl
halides,
205 [223].
underwent in situ aldehydes.
The product
metalation
ketones.
nitriles
from such
as evidenced
and epoxides
[224].
by con-
205
204 Diazo compound 206 has been metalated 207 [225]_ tones
This lithiated
to afford
species
208 (65-8OZ)
by n-butyllithium
has been reacted
at -100”
to give
with benzaldehyde
and ke-
which has then been converted
to epoxides
and al-
dehydes _
OH
298
207
206 Theunderlinedallenic ated by n-butyllithium
hydrogen atoms in compounds 209-212 and subsequently
replaced
by alkyl
groups
H
Y qzC’C’$JHOH
have
been metaf-
[226,227].
,CH20H
‘C=C=C \
H’ =
ti
CH3 210
209
? tH3 (RO)*P-N-C;&* 211 Terminal acetylenes with n-butyllithiom ides
to afford
electrophiles lithium
214
with propargylic
to give [228].
hydrogen atoms have been dimetalated
213 which reacts Such alkylations
at the terminal
carbanion
systems have been condensed
regiospecifically are
to yield
with cuprous
to give octamethylcyclododeca-1.3.7.9-tetrayne [230],
respectively. Li
RA
*
213 Turning
stituents
[231].
by reactions
215.
Other acetylenic
chloride
[229]
and acetic
acid-D-d
RA,
‘E
’ Li compounds,
by n-butyllithium
The following
to
214 a large ascertain
order
other
carbon-
R’
RA, . Li
hal-
uith
and monodeuterioacetylene
R’
to aromatic
were metalated
with alkyl
followed
number of a ranking
215 p-substituted of
has been established:
anisoles
ortho-directing
-S02N(CH3)2.
-S02NHCH3, -CONHCH3,-CH2N(CH3)2 =- -0CH3 > -CH2CH2N(CH3)2. -NME2. -CF3. F.
sub-
33 Similar
results
The effect
were established
of TMEDAin such directed
.A regiospecific
route
o-metalating
and hydrolyzing benzamides
several
was studied.
aryl
ketones
the carbonyl
with n-butyllithium, been o-metalated
has been effected
by
group of :i,:i-dimethylbenza-
condensing
The mathod is illustrated
[232].
have also
o- and m-substituted-anisoles.
metalations
to o-substituted
reagent, = across
adding organolithium mides.
for
with various by 216,
and condensed
electrophiles,
217, and 218.
with electrophiles
Thioto afford
219 [233]. LiO
5
0
R
LiO
R :I(CH3)2
Metalation
of several
has been shown to give ganolithiun
reagent
parent methylenedioxy
220 [234].
223,
of these
lithiated
The site
with dimethylaminomethyl. of the ring
stituted
thiophenes
Z,!i-disubstituted mediates
225 [237].
metalations
of thiophenes
and carboxamides [236]_
substituted
was shown to be a Thus, 2- and 3-sub-
in the 5- and 2-positions,
systems were metalated
[235].
with electrophiles.
of the substituents
were lithiated
were condensed
Other directed
directed
Or-
exchange of the correspond-
to 222 at ambient temperature
were condensed
methoxymethyl.
position
compounds by n-butyllithium
and 222 L-2351, respectively_
from metal halogen
isonerized
species
of regiospecific
function
221 [234],
prepared
ing bromo compound at -78”. All
219
218
217
216
respectively;
only at the 3-position_
Such inter-
with electrophiles-
metalations
methoxymethylferrocene ,N-Ph Ph2P_--
224
have been effected [238],
on imides
and ferrocene
225
like
226 to give
224 to give 227 [239].
34
227
In other work dealing duced by reaction of
with metaiation
I-methyl-5-methoxyindote
tive
giving
1inked polystyrene
organolithium
has been ring
and chromium species
followed
[241].
Also.
cross-
with n-butyl f i thium-WED& [2-‘2-2541
228 has been converted
with t-butyltithium
and 1ithiation
has been found to be nonse!ec-
intermediates
t i ttiated
benzyne has been oro-
with LiTXP [240]
with n-butyllithium
three different
metafation
of aromatics,
of phenyl benzenesulfonate
to 229 (G = Si:,
by condensations
CO2Li, others)
by
with electroohiles
[245]. (Ph)Cr(C6F5G)
(Ph)Cr(C$5H)
229
228 Metalation give
231 to afford oxide, [24S].
of arylsulfonylhydrazones
vinyllithium
reagents
like
232 have been realized
aldehydes,
ketones,
230 by organolithium to be studied.
with dimethylformamide
and alkyl
X-!iHAr
R
like
231 continues hatides
[247],
[246],
)I
to give
like
233 have been treated
234, apparently
via ring-opened
Other examples are cited.
233
232
231
a-Epoxytosythydrazones phenylcopper
YE
Ri
R’ 230
carbon di-
PA
ji R>
to of
and chlorotrimethytsilane
R\;/Li
/
reagents
Condensations
234
with n-buty3lithium intermediate
235 [249].
and
Other re?+ted chemistry olefin
tosylhydrazone
of this
formation
functional [250],
methylbicyclo[4_1_l]oc afford
chemistry
the use of
this
ta-2,4-diene
diethynylcarbene
235 [252]
volving
the conversion :
for
nitrogen-containing Sy metalation.
ketones
aive
carbodiinides.
5.
LITljIUW
Lithium dichloroalkoxides
245 [260].
XD
while
to possiblv control
[25”],
239 [256]
dianion
242.
to give
Carbenoids
studr
(CH)12
hydrocarbon
R-X
242
at
170-209
nonto
O?.GR~~OLITHIiiYS
Subsequent
and the
treatment
a convenient
243 and 244 have also
Lithium dibromomethide
have also
donor and reduces
242 (X = Br) [259]
RUX’ x
and 249 [257],
have been added to ketones
241 [253]_
like
to afford
of an unusual
241
of mi-
and in a
1&C! decomposes
HALCGE!4-SUESTiTiJTED
and dibromomethide
and aldehydes
X
of
of 7,7-di-
238
species,
OTHE3
silylated
respectively_
the synthesis
bridge-bending
(X = Cl) or LDIPA (X = Br) provides like
with ketones
pyrolyses
Reagent 239 is a hydride
to alkoxides
CAP.fiEFOIDS
dihaloalkenes
[251],
237
iwo other
n-butyllithium
in the preparation
of 237 to 233 [255].
236
resulting
reaction
with the stereo-
to the regiospecificity
and to study stereoelectronic
12531 and as part of a test
been prepared
relation
fro::; *:-pinene
gration
enolizable
has been concerned
group and its
route
with to l,i-
been condensed
and vinyl
sulfides
has been employed ES part of [261]. CHO 25\::
/
C,H5D
\8rBr 243
Li
in-
36
c2*50,: SPh
/p X Cl
C2%0
A variety noids
\Li
of cyclopropanol
derivatives
Thus, treatment
[262-2641.
amides [26_3]. and 2-chloroethyl with large
[264]
numbers of alkenes
246 have been prepared
of 247 where R = alkyls
and acetylenes
to afford
246.
In the area of cyclopropyl 251 [265].
In a related
The preparation
study,
exchange [266].
Other examples of this
alcohols
addition
or diethoxymethyl,
then alkylated
of copper
249 (R = Irethyl,
via nucleophilic
Br
249 (R = vinyl
carbenoids,
to 250 by t-butyllithium,
by methyllithium cyclopropy?
248
247
R’ = H) has been converted cussed_
and
Li ROCCl2
246
to give
via carbe-
esters
with LiTMP gave 248 which were condensed-
RO u
lyzed
[262],
reagents
or hydro-
from 251 is dis-
R’ = COCH3) was converted
to the carbonyl
stereospecific
to 252
and halogen-metal
synthesis
of o-bromo-
are cited. Li
8r
R”
8r
Br
Br
LR: &y .&R &c*3 I< .R*
251
250
249
Carbenoids
containing
pared from 8,8-dibromo-
c2711. others
were thermolized
reagent
annelated
tyllithium
[272]-
[269] to six-,
OH
been pre-
or converted
Cyclization
have been realized
[267,
2nd nonenes [270].
seven-,
were condensed
and gemi-
and eight-membered
with
electrophiles
rings
while
to allenes.
253 has been generated
and a dichlorodisilane
cyclizations
have similarly
and 8,8-dichloro-3.5-dioxabicyclo[5_l_O]octane
Some of the above species
Organolithium
252
endo-lithium-exo-halogen
266].9.9-dibromo-cis-bicyclo[6_l_O]nonanes nal dibromocyclopropanes
\
followed
from the corresponding
by metal-halogen
of 253 led to 1.2-disilacyclopropane on bis(sily1)
bromolithium
exchange with n-bu254,
Other
system 255 with dimethyldihalo
derivatives of silicon, germanium, and tin to afford 256 [273].
3i
si\SiLC’ \
‘Li
254
253
257
256
258
(M = Si.Ge.Sn) Finally, to give verted
lithium
dichloromethanebot-onic to 258 by mercuric
to be useful
acid
has been condensed [274],
and vinyl
bromide [275]_
in transferi-ing
with trimethylborate
system 257 has been con-
Mercury reagent
isopropylidene
carbene
253 has been shown
to olefins.
ADDITIO:: AND SUBSTITUTIONREACTIONS
6.
A simpler dardization
method :han double
of alkyllithium
through a syringe acetic is
dichloromethide
acid
solutions
of butyl-
in THF until
titration
has been suggested
[276]_
tire yellow
procedure
ihe
or methyllithium
for
the stan-
involves
addition
to a weighed amount of diphenyl-
end point
due to dili+hiodiphenylacetate
reached. In the area of aliphatic
lithium
initiator
two equivalents
soluble
and aromatic
of n-butyllithium
The initiator
organolithiums,
to one equivalent
alcohols
alcohols
to give
allenic
lithium
to 261 and subsequent
of styrene
259 have been found to react
269 [27G].
Similar
hydrolyses
additions
to ally1
di-
by adding
of m-divinylbenzene
has been employed in the polymerization
Alkoxypropargylic
an efficient
in benzene or heptane has been achieved
with n-butyllithium
of butyl-
alcohols
[277].
and isoprene. and benzyl-
are discussed.
CH30 R+
=
R’
OH 261
260
259
Both ciscloalkenones
Fh----
TOH
and trans-lithiocyclopropanes
262
such as 263 to give vinylcyclopropanes
Functional ized
cycloheptanes
are thenobtained
have been added to alkoxycvsuch as 264 L279]-
by heating
264.
3s
OR
Tandem phenylation further
investigated
ketones trated
264
263
262
by phenyllithium-reduction
as a method of converting
to S,v-unsaturated by the sequence
aromatic
by lithium/amnonia %,2-unsaturated
hydrocarbons
has been
aldehydes
The process
[ZSO].
and
is illus-
265 - 266 - 267.
266 Phenyllithium to afford
and related
ketones
like
reagents
268 and esters
ed to z,.,“-butenolides
to give allylic
tain
at sulfur
sulfonate
boxylic
acids
esters to afford
sulfones
and carbinois
the nitrile
triple
via the intermediacy
[283],
[284],
Ar
/i
Ar’
and added to an aminoketone [285]_
by addition
In contrast
and methyllithium
Such reactions
In a different paper, ketones and non-enolizable nitriles [287].
R-k-
R-LNLi h
N\
lb- /
r
N‘Li
to earlier tetraene
results,
condensation
and diazomethane 275 [288].
proceed were syn-
&-’
273
272
_
with carbon dioxide
274 and non-cyclic
of butyl-
[286].
NH 271
with cer-
combined with car-
of 272 and 273.
NH
been add-
reacted
270
bond of arylnitriles
from pyridyllithiums
R-\t lithium
They have also 270 [282],
269
Enamidines 271 have been obtained
thesized
like
ofdibenz[b.f,l]azapentalenes
268
across
269 [281].
alcohols
to yield
ketones
as part of the synthesis
have been added to perfluoroanhydrides like
of cyclooctatetraenedi-
has been shown to give
tricyclic
39
275
274 Interaction been reported [289]_
of pyridine to qive
In contrast,
pyridine
reaction
gave mostly
:*ith those
obtained
278.
with metal-free
P-n-butylpyridine
n-butyllithiun
(276)
between n-butyl
277 and less
chloride
than 1% of 276.
and lithium
The results
Derivative
with magnesium species. l.fi-
in pentane has
but no 4-n-butylpyridine
metal in
are compared
277 might arise
from
. -.
_ ‘,
A
$+..A,
,i
W
Q
V
(277)
t ‘I
Li
276 Cyclic thioethers attack [290].
at sulfur
like
by t-butyllithium
The driving
force
for
to afford
such reactions Attack
benzhydr:;l ic carbanions
1i ke 281_
been realized
282 and its
dioxide
on thiete
derivative,
phinodithioate
esters
respectively like
278 ones have been found to undergo
277 279 and related
is ascribed
at sulfur
l,l-dioxide
[291],
ring opened products
by organolithiums
tc give
283 and its
and at the alkylthio
284 to yield
phosphine
sulfides
sulfur [292].
fi
,
..
\
I Ph279
Ph 280
281
Ph2P-S-R 5 282
like
280
to the stability
284
of
has also related of phos-
40 Epoiyethylsilanes tetraphenylsilane was determined
like
diisobutylaluminum
g-alkoxysilane acid
and anti-elimination
_.
J\
288 and 289,
respectively
12943.
arose
(RI” Li)
in THF or ether while
respectively_
is a function
of solvent
289 and ketals
[2g5]_
Thus, 291 OSiI
0
RARm*
R”
R’ ”
290
A variety
hemithioacetals
292 is formed in HMPAor TMEDA.
OSiz
SR
acetic
from syn-
L
288 of 0-trimethylsilyl
of reaction
(290) with organolithiums is obtained
jugated
or glacial
The olefins
R
287 The course
R+
an intermediate
t-butoxide
R)& Si;
using
:Ph
286 287 afforded
to 9-ketosilane
of hydroxy and trimethylsilyl,
+
and trans-286
0
which upon treatmen t with potassium
gave olefins
it
alpha to silicon
on both cis-
amines.
\
285 of methyllithium
Addition
to give
of 285,
are compared with those obtained Ph3Si
?
analogues
the carbon
chemistry
The results
and various
Ph3Si J
attacked
Similar
manner.
trans.-stilbene.
with phenyllithium
Using deuterated
[293].
that the phenyllithium
in a npn-stereospecific gave mostly
285 have been treated
and styrene
of allyl-
and saturated
291 lithium
292
reagents
have been added to con-
enynes 293 where R’ = alkyl [296] and amino or hydroxyl groups [297]. products obtained such as 294 are in contrast to 3.4- and mix-
The 1,2-addition tures
of 1,2-
and 1,4-addition
and magnesfum reagents,
products
realized
with corresponding
respectively_ R
organozinc
R
R”
_--
*i*
Condensation a+-dihaloalkanes
293
of dilithiobutadiene
and other
have been found to give
cyclic
di-
294
and triene
products
tion
at the most negatively
charged carbon atom followed
tion
to afford
ring
the smallest
possible
[2g8].
from 296 and 1,3-dibromopropane.
In other
been employed in the synthesis
of monoterpenes
ium has been added to benzyne addition products [300].
by secondary
For example,
papers,
dianions
from initial
alkyla-
295 is obtained
pentadienyllithium
12991,
with alkyla-
297 has
and cyclopentadienyllith-
to give phenylcyclopentadiene
rather
than cyclo-
=
0
__ - -. -._ 2LiC (4
295
A variety Among those
of annulenes
continue
to be synthesized
formed were 1,8-bisdehydro[14]annolenes [302-3051,
addition
with lithium
298 [308].
In contrast,
specific;
for example,
erythro
ratio
_-
giving
similar
a lrl
additions
the latter
reagent
have also
afforded
with a threo-
pyrimidine
derivatives
like
of certain
enolates
vinylogous
derived
the conversion
300 with chlorobenzamides
302 [309],
prostaglandins
in HMPA/benzene/ether [314].
like
trihalides
have also
been
[311,312].
303 by carbonyts
and other
electron
304 have been synthesized Such reactions
[313].
Methyl ethyl kinetic
like
and with Group ‘J
Such organolithiums
from 305 and ketones to their
) 32
ii
stabilized aldols
of 306 to 304.
been converted
6-hydroxyketones
y’jN(Cii
302
Turning to organolithiums groups,
0
been condensed
301
have also
alcohols
the cis-alcohol
Li
303 (M = P, As, and Sb) [310].
employed in the synthesis
tute
of the cis-trans
299
Lithium acetylides
kinetic
and
of 299 and 300 were more stereo-
ijOLi
-Y
298
withdrawing
[306],
of Sri_
Ph
to yield
acetylides.
was found to be non-stereospe-
mixture
0
301 to give
lithium
6,8,15,17-tetrakis-
[307].
to 2-phenylcyclohexanone
acetylide
using
[307],
a 6,17,23-trisdehydro[ZZ]biannulene
a 2.4.13.15-tetrakisdehydro[ZZ]annulene Carbonyl
Lif
207
295
dehydro[18]annulenes
cific
(&AJ-
enotates
and methyl propyl by lithium
and then condensed with aldehydes
using constiketones
diethylamide
and ketones
to give
0 i’
OH R6
A/+‘.
CH3- =
R”
R
The enolates annelating enolate
of several
reagent
to yield
310 via C-alkylation gave only 0-acyl
Sulfonium ylides butyllithium variety acids
been
[320],
The chemistry
of aldehydes. by certain
have also [319],
halides
of 309 with acyl
to yield
ketones,
esters,
to 312 by
313 [317].
nA
and carboxylic chlorides
and sulfenyl
sulfur,
disulfides,
313
and used in the total of dilithio
than y-products
( 2 fb - \..
and angelic
= 2Li+
0
1
illustrated In contrast,
acid acids
[322].
halides
anhydride
catalyzed
to give
of sativenediols
of a.&unsaturated
317.
314
by nethylene
synthesis
only y-products
and 3-methylcrotonic
c/”
salts of salts
317 [322,323].
gives
tiglic,
been alkylated
condensed with citraconic
Thus, alkylation
in such reactions
_&
and acylated
312
be studied.
R
with alkyl
reaction
314 [318].
butenolides
c-
has been treated
In contrast,
[316].
enolates
Ketone enolates
butynoic
(309)
with bi-
The lithium
311 (R = CH3. OC2D5) have been converted
thiolated
by cuprous chloride
senecioic,
have been condensed
compounds 308 [315].
derivatives0
311
H
tricycle
or LDIPA. then alkylated
of lithium have
to afford
(316)
cyclohex-2-enones
307 to afford
of cycloocta-2,4,6-trienone
chlorides
306
305
304
acids
continues
by 315 afford
studied
and 3-methyl-2-hexenoic,
[323]. R
k R’7 316
cuprates were 2-
crotonic.
R R>,/.
C02CH3
C02CH3
315
to
more cr-
the use of lithium
Among the acids
two
[321].
317
43
Trilithioitaconic
acid
to afford
u-nethylenelactones
similarly
been reacted
6-n-hexadecalactone
(318)
has been condensed with aldehydes
like
319 [324].
with certain
chiral
Dilithiopropiolic
epoxides
to give
and ketones
acid optically
(320)
has
active
[3X].
Li C02Li
Li02C
Li
ADLi
-EE
D. 318 Related 3273,
319
salts
coupled
of acids
have been oxygenated
with formaldehyde
Monoalkali
[329]. esters
320
carboxylate
[3X3].
with molecular
and condensed
anions
oxygen [326,
with carbon disulfide
have been directly
alkylated
A full of esters
paper appeared describing and ketones
cycloheptancne
(321)
[331].
sulfenylations
The process
and dehydrosulfenylations
is illustrated
by the conversion 0
SPh sodium meta-
LDIPA PhSSQh
periodat?
)
322
321 Lithium enolates bromomalonate
esters
by displacement
bine by conjugate
323 Benzylidene yield
of
to enone 322. 0
occur
to yield
[330].
of alkylidene like
succinates
324 to give
products
(323) like
of 323 on bromine to afford
have been condensed with 325 [332].
malonate
The reactions
anions which recom-
addition-elimination.
325
324 derivatives
of glycine
326 which can be alkylated
to give
esters
327 [333].
to 328 thus finishes
the overall
Potassium
may be employed instead
t-butoxide
have been lithiated
conversion
by LDIPA to
Simple hydrolysis
of “glycine” of LDIPA.
ph_--.z
Qfy-F.=
R 326
327
of 327
to higher a-amino acids.
328
f-l
Several cinimides
a-ltthioesters
like
and nitriles
329 to yield
papers, ethyl lithiofarnesoate oxygen and a-thiomethylation lithiodiazoacetate
products
0
C02CH3 I
o-~~ 1 ‘I’”
330 [334].
has been found to undergo a-hydroxy?ation
CH2G 0
[335],
with
and ethyl
332 [336].
c& d BF4-
N2CC02C2H5
330
331
332
derived
from phosphorus
esters
and amides have been employed
Reagent 333 has been condensed with 310 (R = H) as part of the syn-
as follows.
of a 1,5-methano[lO]annulene
system [33?]
and reagent
334 has been added
to ketones taining
suc-
In other
C0*CH3 329 Organolithiums
like
with methyl methanethiosulfonate
has been added to 331 to afford
&zA
thesis
have been added to N-protected
polyfunctional
as -part of a new spiroannelation leading to quaternary Oiethyl-l-‘alkyl-2-oxoalkanephosphonates cyclohexanones [338]_
prepared
by alkylation
a-copper
reagent
of 335 followed Finally,
[339].
been found to be stereoselective depending
upon the solvent
by acylation
condensations and give
of a subsequently
prepared
of 336 with acetophenone
different
and the presence
carbon-conhave been
diastereoisomers
or absence
of
lithium
of
have 337
bromide [340]_
0
334
333
;
335
Li
(CH3)2N’pl+ph cH3 337
336 N,N-Disubstituted by lithium
amides and N-substituted
dialkylamides
in HMPA, then alkylated
and 339, respectively
[341]_
selenenylated
products
to give
Lithiolactams like
lactams
have also
340 [342].
have been a-lithiated
to afford
species
like
been sulfenylated
338 and
Reaction
of
posed to yield
340
339
338 lithioacetonitrite
intermediate
and retated
compounds with 341 has been pro-
Some chemistry
342 [343j.
of 342 is discussed.
Li+ -tr(C0)3 342 Other tithionitriles sitytated
[348].
have been hydroxylated
and employed in the synthesis
%-Metatated
isocyanides
hydes and ketones
to give
to 345, methanotysis
like
R = hydrogen, like
of which yields
‘and R’ =
343 have also
343 (M = Li,K)
intermediates
pyridyl
,
been condensed
and with carbon disutfide
to give
affording
347 which,
to 346 when M = K,
formamides
to yield
[351]. affords
.
343
344
345
346
347
348
Under the topic like
[352]
348 [353].
M
=c
of miscellaneous
of nitro
lithio-2-nitropropane
nitrosopyrrolidine
Species
3-amino alcohols
upon methytation,
M
the displacement
with alde-
compounds cyctize
Both 344 and 345 have been
345 is converted
with epoxides
[346,347].
[349].
The latter
P-oxazolines.
ultimately
atkytated
have been condensed
344 [350].
In contrast,
trapped with electrophites.
[344,345].
of S-cuparenone
(349)
nitrogen
groups of p-substituted
compounds,
synthetic
nitrobenzenes
in tMPA have been published and 2.5-dialkyl-N-nitrosopyrrolidines
[354].
details
of
by reagents a-Thioethyl-Nhave been syn-
-16 thesized fide
from the lithio-N-nitroso
[355]
and alkyl
of products
arising
halides
compound and ethyl
[356],
respectively.
methoxycarbonyl
Finally,
dtsul-
the wide variety
from dilithio salt 350 and certain acid chlorides, chloro-
acid chlorides, and chloroesters has
been described
[357]. ki
Ph2C-NPh Li
Turning to sulfur-stabilized been conveniently-metalated condense w=ith aldehydes are useful describes
organolithiums.
by LOIPA in THF-HMPAto give and ketones
to afford
in the synthesis
of 1;4-diketones
the use of 353 for
cyclopentanone
of an earlier
method such as low yields
lithium
[360],
(354)
351
of vernolepin
fonates
of primary alcohols
reagent
[363].
Phenylthiomethylhave been used
to afford
of fraudulent
branched-chain
sugars
respectively.
355
354 alkylated
added to 356 to give
fluoroborate
351 which compounds
in which the limitations
355 [361,362]
353
358 [365],
have
Another paper
and cyclcpentenones. formation
have been conveniently
with-tropylium
like
The latter
and n^-phenylthioketones,
352
P-Lithio-1.3-dithianes
sulfides
species
352 [358].
are overcome [359].
and bis(phenylthio)
to prepare a precursor
phenyl vinyl
with arenesul-
357 [364],
condensed
and employed in the synthesis
from certain
ribofuranosides
[366].
OR’
0 356 Monolithiated
s-trithiane.
357 tetrathiocane,
358 and pentathiecane
2, atid 3) have been condensed with carbon dioxide, disulfide
to give
sulfur
‘CH-5/ 2
(n = 1,2,3)
n = 1,
and carbon
360 [367]_
s/(CHrS)o\CHLi 359
(359,
dioxide,
360 (I-I = 1,2,3)
(S02Li,
CS2Li)
Lithiodithiane
361 adds
in a l&fashion
362, a compound
which
subsequently
alder
[368].
Dithiane
reactions
ketones
to give
conveniently
enters
361 also
ketene thioacetals
converted
ii
into
like
CH3
to afford
condensations
The latter
and Diels-
aldehydes
and
compounds are
with NCS or iiBS.
CA
361 Interaction
into Michael
has been added to other
363 [369].
n-haloesters
Si:
to Z-nethoxyacrolein
363
362
of 364 and 365 has been shown to afford (RI- and (S)-4-hydroxyFinally, tris(methylthio}methyllithium (366) has been [370].
2-cyclopentenones
employed in the synthesis
of dl-protolichesterinic
acid
[371].
CH3S
Li CH3SO/
Lithiation
of epoxysulfones
368 [372.373]. stead
Interestingly.
of n-butyllithium
Epoxynitriles
like
367 leads
metalation
to cyclopropyl
cyclobutyl
products
of l,l-dilithio
ii
[379]
have been alkylated
and with epoxides
PhS02XPh
Li2CHSON(CH3)2
like
372 have been converted
371 to a-selenoaldehydes
373 (G = R) by acid chlorides, 373 (G = 0CH3) by methyl chloroformate , and to a-selenoacids
OH) by carbon dioxide ketones
ultimately
and con-
[380].
373 (G = H) by OMF, a-selenoketones esters
[375-3781
Li
370 a-Selenoalkyllithiums
[381].
affords
in-
369 [373].
systems 370 and 371 has been reported
of monolithiosulfones
densed with carbon disulfide
like
369
368
A variety
like
[373].
367 chemistry
derivatives
of 367 with methylmagnesium iodide
or LDIPA affords
behave similarly
Additional [374].
366
365
364
Similar
treatment
a,B-unsaturated
a-seleno373 (G =
of 372 with a,?-unsaturated
epoxides
[382].
4s
I
R” Li
G
RSe%
0 373
372
Methoxyvinyllithium denced by its
reaction
(374)
and 3-hydroxy-2.4-pentanediones lithium
(375)
the first
has
been
A / esters
with
like
halosilsnes
C- or S-alkylated
products
afford
381 is described-
[388]. to yield
Lithium reagents
is observed
to give
to nive
employed [387].
380 with several
epoxides
to
The related
trimethylsilyllithiun
381 [389].
Subsequent chemistry
382 (M = Si.Ge.Sn.
of
and Pb) have been cou-
383 in which retention
of the double
bond
[390]. R3MLi
:M
OLi
n.-.-
HETEROCYCLES Several
large
Lithiosilyl-
have been alkylated
upon the electrophile
has been condensed
olefins
chlorides
alcohols
to the corresponding
379
has been added to cyclohexenones
7.
hydrolysis,
376 to sive
was studied.
by metalation,
depending
Dimethylphenylsilyllithium stereospecifically
/
after
with aldehydes
of the reaction
378
377
Zji n.
[333]
ethoxyvinyl-
0
compounds were converted
and the stereochemistry
configuration
afford,
376 [385]. Li
379 and amides 380, prepared
pled with crotyl
to
as evi-
dihydroxyacetones The related
respectively-
375 377 has been condensed
The latter
378 [386].
chlorides
condensed
to give
OCH3
374 Lithiovinylsilane like
and esters
[384],
stable acylsilanes Li
to b e employed in synthesis
continues
with ketones
papers discussed
number of N-substituted
nicotinic
acid
to determine
derivatives
the extent
certain 1,2-,
aspects
have been treated and position
of dihydropyridines.
1,4- , and 1,6-dihydropyridine
Thus, a and dihydro-
with LDIPA and potassium
of metalation
[391].
Although
t-butoxide
the pyridine
49
derivatives afforded
gave little vinyl
or no metalation,
organolithiums
denced by deuteration Li
like
@yR
p-
c kH3-‘Li 385 1.2-dihydropyridines
384 In contrast, V-unsubstituted and the anbident
pyridines
organometallics
like
alkyl-1.2-dihydropyridines
388 [392]_
involves
with
Incidentally.
the conversion
sized
by alkylation
reduction
The direction
is discussed.
and aryllCthium
of base-cataly
In another
to.afford
and temperature
54ithiouracil
either
derivative process
394 34ethylquinoline THF-HMPAto afford
FM-
p
78
-T \
Li
390 xhich. have been synthe(391)
zed aldol
2,2-bipyridyl
followed
cyclization was treated
392 OF 393 as a function
by Birch of such di-
viith alkyl-
of the stoichiometry
- 393
394 has been found to rearrange
to 395 [396].
rearrangement,
cause of the high electron OSiz
to give
[393].
392
an intramolecular
halides
paper,
to give
of :I-
i395] _
391
went a similar
389 o f 1,5-diketones
of 2-lithiomethyl-Gnethylpyridine
[394].
ketones
electrophiles
a new synthesis
i0p3
388 a series
387 paper described
CH3 386 387 have been I:-
of 389 to 330 by methyllith-
the corresponding ii-alkyl derivatives /- *‘.<, E/' fl ‘I ,-= C .. :;,.A; ci, '\,& :;., ,.' A
. ._st...‘.x Li
like
condensed
ium and heaxing
ii
1
H !
it
i
CH3
A full
compounds
and CR) as evi-
H
-. Y’--‘.H
s-substituted
acid
(R = carboxamides
experiments.
i,H
lithiated
the dihydronicotinic
384-386
Although
dilithiocytosine
density OSiz
397 was stable
for
396 the first
OSiz
397 time using LDIPA in
398 which was condensed with aldehydes. Similar
treatment
via
396 under-
presumably be-
on nitrogen. LiNSiz
395 has been metalated
399 [397].
apparently
dilithioisocytosine
ketones,
and alkyl
of cycloalkenoisoquinolines
400
50 yielded
mostly metalation
when n = 5,6 [398]_
products
In contrast,
401 and little large
or no addition
products
amounts of 402 were realized
402
when n =
398
&-Jy
@qy -4
>i
Li 403 has been metalated
to give 404 [3g9]_
followed
by condensation
Ph
402
401 Tetrahydroisoquinoline kylated
;“’
Metalation
of either
with aldehydes
by n-butyllithiun,
then al-
403 or 404 by sodium hydride
and ketones
afforded
405.
::J-6Jq* ::Jx---qj RA
‘P(OC2H612 // 0
monolithio
(406)
or dilithio
by treatment
two equivalents
of LOIPA in THF/HMPA[400].
afford
a variety
aY 0
Perimidines mostly [401]_
products
405
(407)
may be prepared trophiles
P(OC2H6)2
404
403 Either
// 0
0
like
of 2,3-dinethylquinoxaline
of the parent dimethylated
heterocycle
Subsequent condensations quinoxalines-
of 2,3-substituted CH2Li
o
LCH
with one or with elec-
! ;ycH2Li
T‘f \wlCH2Li
3
406 like 408 react
In one case,
salts
with alkyl
407 and aryllithium
409 which arise
by addition
ring
occurred
lithiation
reagents
of RLi across
to afford
to give
the C=K linkage
410 in low yield.
51
408
409
An unsuccessful bases
like
desired
attempt
phenyllithium
412, mostly
410
411 to 412 via 413 by means of strong
to convert
has been reported
411 was recovered
despite
ArChzlJ
ArC”=llufl 0
by metalation,
cyclized I
is higher
‘C02R
cyclizes in their
by copper(I1)
413 to 415 with or without
presence.
The related
hydrolysis
copper(I1)
non-benzo
sys-
415 acid
but not LDIPA, to give electrophiles
Lithiated
‘C02R
’
fluoride.
4,5-Dihydro-1.3-thiazoli-4-carboxylic
Thus, a full
zn
have been described [403].
414
with various
the
by D20-CD3C02D.
412
prepared
n-butyllithium,
of obtaining
ArCn=f
examples of heterocyclotetraaromatics
salts though the yield tern was also
quenching
rfi
411 Thus, 414,
Instead
0
‘C02R
Additional
[402].
416 oxatolines
to give a-substituted
has been dimetalated
by
Subsequent condensations products
are described.
417 continued
paper described of which affords
(416)
417 [404].
to be extensively
the alkylation
oi chiral
S-o-alkylalkanoic
acids
investigated
in 1976.
system 418 to give 419. 420 in enantiomeric
purity
52 of
45-85% [405].
alkylation
of 418 (R = H) gives
order of introduction yields
sequential
Interestingly,
(S)-(t)-420
of alkyl while
stereoselectivity
(R)-
halide-lithium
cation
entry
dependinq
upon the
nethylation-butylation
affords
to an underside
and two-fold
metalation
acids
For example,
groups.
butylation-methylation
is ascribed
to 418 via initial
either
two-fold
or (S)-
(R)-(-)-420.
Such
of the alkylating
agent
complexation-
Ph
=Q/
RCE
0.. 1 Lie&H3 418
419
Lithiooxazoline nition
418 (R = H) has been found to be capable
towards racemic
mides and iodides
halides
kinetically
in the R enantiomer
enriched
3-alkylalkanoic allows
are
alkyl
acids
(420)
the establishment
Thus, racemic
[406].
resolved
by 418 to give 419 which,
and oxazolines
likewise
enriched
of absolute
of chiral
secondary unreacted
alkyl
upon hydrolysis,
in the R enantiomer.
configurations
of secondary
recog-
al kyl brohalides
afford
The procedure alkyl
halides
and 420 using only 418. Chiral mine if
oxazolines
they might also
[407,408]_ anoic
Butylation
acid
(420)
[407].
of nihutyllithium
technique
of conjugate
containing E4°g]-
serve as suitable of 421 followed
though the authors
the R configuration dition
421 and 422 have been derived
systems
precursors
by hydrolysis
predicted
Conversion and hydrolysis
425 to yield
A,
to optically
the acid
should
gave (S)-f+)-424 has also
methoxyacids
to deteracid
acids
gave (S)-(+)-2-methylhexhave possessed
of 422 to 423 followed
addition-hydrolysis
like
front L-serine
by conjugate
(4081.
ad-
The iatter
been employed on methoxylike
426 and their
q
lactones
‘“=$--9+
CiCH3 421
i)CH3
422
423
Ph
424 Related 428 via
426 oxazoline
429 [410]
responding
2-brnzoyl
by LDIPA to afford oximes [412].
chemistry
included
and the autoxidation derivative
431 and 432;
[411]_
the conversion
of
of
430 by molecular
P-Isoxazolines
427 to thiiranes oxygen to the cor-
have also
the former compounds fragment
been metalated
to a,$unsaturated
R \ \ .. N-
R@-I
427
430
Metalation (436)
isoxazoles
of
and methyl group
on these
(435)
423
429
431
432
433 and 434 by n-butyllithium lithiation
f413].
yielded
In contrast,
Li
both ring-
the use of LDiPA
systems gave only 435.
o-at3
/
433
434
Oxazine deriva:ives
437 and 438 have been found to react
ketones
and aldehydes,
to afford
respectively,
Thus. 437 gave 439 while
437
434
438 afforded
with aldehydes
stereospecifically
to give
[414].
440
439
441 has been lithiated,
and ketones
olefins
440.
438
Thiomethyldithiane
436 with unsymmetrical
esters
then alkylated
or a-hydroxyesters,
or condensed resoectively
[415-J.
1,3-Dithiane-l-oxides have also been metalated and condensed with elecThus, 442 with LDTPAafforded a Z-lithio derivative arisin9 trophiles [416]. from preferential Tithio
salt
by a factor densations
abstraction
with certain of 3-4:l.
of the C-2 equitorial
electrophiles
occurred
Other stereochemical
cis
results
of 443 (R.= CH3 and Ph) with electrophiles_
proton.
Reaction
to the sulfoxide are discussed
for
of this oxygen the con-
6-l
Q
c-Jo
R
H
CH3S
A large of
l urophenes
number of papers appeared lithium
derivatives
of
to allenes
certain
2,5-dialkyl-3-lithio-thiophenes
stituted
thiophenes,
like
containing
additional
selenophenes.
446 [417].
occurs
447 (M = 5 and Se) [418-421]_
ble and do not open [420,421].
chemistry
Similar
andselenophenes
2-chloro
Such ring openings
have been employed in the
446
445
=\_
i
3-halo
compounds have also
of strong three
bases in polar
position
on the sulfur discussed. ford
been described. gives
of the heterocycle
[423].
of the side-chain
dilithiobutadiene
[424].
Condensed
to give
products
without
Thus, treatment
of
of 450 by a variety at the
Products arising from substitution and abstraction of a thiomethyl proton are
452 as evidenced 453,
454.
in which the selenium-
SCH3 450
-\,
the intervention
by condensation and 455 also
has been found to afwith electrophiles open with methyllithium
but not the sulfur-
containing
[4251_
CR3
__-
--KH24,-’
447 (R = SCH3) via metalation
of 451 by n-butyllithium/TMEDA
selenophenes
-=
449
such ring-openings
solvents
Metalation
are cleaved
.-
448
447 of
3-
groups are sta-
&Z-A, Ar
444
examples
sub-
In contrast,
Ar*Ar
other
of
to afford
and 2-dimethylaminomethyl
of 448 to 449 [422]. Li
Several
ringand tel-
444 have been found to open even
445 and ketoacetylenes
vinylacetylenes
lithiothiophenes conversion
in 1976 describing
furans.
_ Thus, 2,5-diaryl-3-lithiofurans
at -65”
%i 443
442
441 openings
Q.
Ph 451
452
rings
55
m
w Other papers
concerned
the rearrangement
gen-metal
with organolithiums of tricyclic
exchange reactions
paration
455
454
453
scribed
y-J---J
of Z-chloro-
and the preparation
and heterocycles
systems
of a variety
like
of dihalothiophenes
and 2-bromotellurophenes and subsequent
have de-
456 to 457 [426],
the halo-
[427],
the pre-
from 2-lithiotellurophene
silylation
of 458 and related
[428],
compounds
CS29] -
R’
R'
ii
457
455
1 . 456
a.
COPPER-LITHIUM Propargylic
461 merely Similar
reactions
than water.
AND 0THER"ATE"
CMPLEXES
459 have been converted
acetates
by running
Intermediate
REAGENTS
the reactions
on propargylic
ate complexes 0
acetals
462 gave ally1
like 464 have been trapped
-
like
463 [431].
by electrophiles
other
-.-R
>
I
R
111
460
459
H-
acetals
460 or
[430].
I‘
R'
R-=
by R2CuLi to either
at -loo and -SO", respectively
= \
oC2H5
462
Methyl propiolate 465 to afford
466 [432],
[433].
Similar
tylenic
ketone [433].
self followed iodides
[434],
have also been
464
463
products
has served
were obtained Related
by condensation and on allenic reported.
as a co-reagent
and to cyclopropyl
of other
electrophiles
ketones
Similar
like
using the latter
additions with
to allenic
cuprates
cuprates
cuprates
468 it-
to give vinyl
mostly
to an allenic
like
and an ace-
on acetylene
like iodine
like 469 to afford
1.2-additions
cuprates
467 to yield
470 [435]
phosphine
56
oxide
have been described
[436].
( *.+C”Li
>=.-\
2
‘P+
2
CuLi
--J
02CH3 467
466
465
=.A*-
cuprates
have also
1437-4391
and with ally1
lustrated
by the conversion
475_
halides
the interaction
Thus, 475 was realized
are il-
472 (R2CuLi) with Z-halo-
474 and addition
[444],
products
G = COR, and !? = methyl [441],
G = COR, and R = cyclopropyl
[442].
but
Similarly,
[443],
X = I, G =
and X = Br, G = C02H or C02CH3. R = methyl
[445].
ALG
A-
have also
476 to olefins
\ 0
0PO(OPh)2 i
476
475
been used to convert
like
477 C4463,
R
I
477
/”
RI
474
473 Dialkylcuprates
J
--Y/G
R
X
479 [447]_
of cuprates
when X = Br, G = COP., R = cyclopropyl
COR. 9 = 2-vinylcyci;propyl
like
acetates
The reactions
olefins.
substitution
when X = Cl,
when X = Cl,
only 474 was realized
esters
to 9ive
compounds 473 to afford
474 was obtained
and n-butyl
[440]
ally1
of 471 to 472 [437].
471 papers discussed
-x,t-unsaturated
been condensed with certain
R
0
Several
470
469
468 Various
enol diphenylphosphate
and ketones
like
478 to ones like
d’ d 478
479
Additional
examples of the condensation
with cyclohexanones alkyllithiums lithium
further
[448].
demonstrate
For example,
di?ithium
add to t-butylcyclohexanone
Reagents
480 also
tion of lithium
to increase
to afford
papers dealing
diphenylcuprate
in the presence
over
and n-butyl-
to -.,S-unsaturated
has been found
1-lrisityl-3-methyl-2-butenone
[449].
carbonyl
the rate of reac-
additions,
of triphenylphosphine;
composed by added ietracyanoethylene
480
reagents
481 in 97% and 86%, respectively_
with conjugate
with
trialkylcuprates of these
tri-n-butylcuprate
have been added in a 1,4-fashion
In other
compounds.
of dilithium
the superiority
the cupraie
is,
however,
Lithium dinethylcuprate
de-
has heen
condensed with pyranosides like 482 to a fford 453 [450], and with oxo-enones like 484 to give 485 via regiospecific intramolecular aldol condensations [451]. OH
R”@ro _
&R
”
H
480
481
482
484
485
CH3 483 Lithium cuprates furan to alcohols to sulfoxides
[453]_
regioselectively
have been found to cleave
486 {P,’ = H or CH3) [452], Lithium dimethylcuprate
added to iron
salts
THF and 2_methylte:rahydro-
and to convert
sulfinate
esters
has been stereospecifically
487 to yield
and
488 14541.
cH3
Lithium cuprates natural
products
spirovetivanes lide
were employed as part of the synthesis
in 1976 including [456],
14611.
dl-sesquicarene [463],
alkylated
recifei
side
organoborates,
on the B-carbon
[457-4591,
[460],
and dl-sirenin
and the acyclic
Turning to lithium
methyl jasmonate
prostaglandins
from Cephalosporium
cockroach
488
487
486
certain [462],
of a variety
and related
a naturally
of
compounds [455],
occurring
macro-
a-methylene-y-butyrolactones
a sex pheromone of the German
chain of several natural products [464]. a 1kynyl trial kyl borates 489 have been
by methyl sulfate,
triethyloxonium
fluoroborate,
and
58
other
active
alkyl
like 49? [455].
halides
and nitriles,
ters, tones,
y-ketonitriles,
y-ketoesters, acid
idation
Details
[467].
instead
upon hydrolysis l_i+
R3B-C-CR’
c=c
/
489
tylenes.
Similar
ployed
to synthesize
been studied prostaglandins
0
[466].
412 after
,YL I!
491
rearrangements
carbon
conjugated _
have been em-
borate
for
494 and with the
reagents
has
the synthesis
(Sia)
of
2_
c:ck*
C-CR’
494
Reagent 489 has been condensed (R” = Sn(n-C41fg)3)which, The use of other chloride
electrophiles apparently
495
with tri-n-butyltin
upon treatment
with formic like
yielded
chloride acid,
to give
affords
trimethylaluminum
491)
Z-olefins
chloride
490 and an isomer since
and
hydrolysis
of Z- and E-olefins.
Z-Brono-6-lithiopyridine afford
ace-
E471.4721.
493
gave mixtures
493 whic$ allyls,
acetylides
( G+
[473].
salts
unsymmetrical
of other
of such reactions
R3B-CX-Li
phenylsulfenyl
492
Intermediates
lithium
Iodination
suitability
R’
= alkyls.
and of 495 [470] diynes.
of appropriate
alkynyldialkylboranes
489 (R’
then affords
of 494 [469]
by condensation
to determine
to give
iodination
unsymmetrical
ox-
of 490 to 2 or E-
R”
Subsequent
es-
1,4-dike-
The use of
to ketones
R’
it
at the acetylenic [468]_
ketones
acids.
490
undergo alkylation
495 were prepared
leads
yield
489 (R’ = H) have been converted to dilithio
Boron reagents trimethylsilyl)
gives
by =-haloketones,
about the conversion
/R’ \
oxidation,
bromide to ultimately halides
by carboxylic R,
after
been alkylated
and y-ketoalkynes
of alkyl
are provided
R2B
corresponding
490 which,
and by a propargylic
methanesulfonic olefins
to afford
Reagents 489 have also
intermediates
tic
acid
treatment
for
the preparation
like
has been added to trialkylboranes 496 which decompose to vinylboranes
of 497 to give
498 illustrates
the utility
to presumably 497 [474].
Ace-
of the method
of pentadienenitriles. N
R2+ s+L CN
BR2
496
h
497
H
H
498
H
59
Trialkylboranes
have also
afford
499 which,
upon treatment
been condensed
idstion
of 500 then yields Li+ :!
with a-methoxyvinyllithium
with hydrochloric
acid,
dialkylmethylmethanols FI
gives
501.
Y
R-81
OCH3
The course treatment affords
of hydrolysis
503 and 504,
respectively_
The boron of several replacement (R”‘X:
iodide
addition ethanes
vinylsilanes
[475],
borate
complexes
synthetically
useful
R” = CH3) followed
and benzvl
Similar halides
505 quent treatment
replacement
yields
by copper such
Thus,
of alkyl
halides
on 506 follonied
507 [478]
and 1,2-diarvl-
chloride
and basic
hydrogen peroxide
Subseaffords
510. SPh f R’ 30-C-R I SPh
Li RC(SPh)2
510
509
508
Yionane ate complex 511 has now been found and epoxides
/U
II/-
506 507 have been condensed with SOS to give 509 [430].
with mercuric
alcohols
is converted
511 in the presence
of methanol and lithium
Reagent 511 al.so reduces
to cis-
aldehydes
between isomeric
capable
of reducing
In the former case,
14821 to alcohols.
methylcyclohexanone
discriminates
acid
respectively_
irialkylboranes
[481]
has been replaced intermediates.
by the addition
(R3BCii3)-Li’
secondary
fhus,
and aqueotis hydrochloric
hydroxide
505 [477]_
of acrylonitrile
501
502 depends upon the pH [476].
nther examples are described_
lithium
to give
on 502 (!? = Sis,
affords
R
of borate
of 502 with aqueous sodium
using cuprous
&
/i
O/CH, 5 530
393
ox-
OH
. -., .Y iJ=
to
5CKl[475]_
ketones
example,
and trans-4-methylcyclohexanol
selectively
ketones
for
like
methoxide,
respectively
in the presence Z- and 4-heptanones
4by
[481].
of ketones, [481],
and
by
60
-reduces
aromatic
and aliphatic
tions,
respectively
[482].
epoxides
act-l-y1
chloride
systems like
ketones with lithium
oosi-
such reductions
formed by reaction
of cis-bicyclo[3.3.0]-
512 in 1976 describing stereoselective trisiamylborohydride
with triethylborohydride
[435]_
[484], The latter
513 reductions of cyclic
and reductions reactions
of alkyl
are useful
tosyl-
in the
of alcohols_
deoxygenation
Aluminum ate complexes 514 (R = Sii) silanes
and used in the synthesis
hindered
after
513.
x 511 Reports appeared a:es
remaining
It has been conveniently
has been shown to be 512 [483]. of 511 with acetyl
at the most and least
The organoborane
continued
with methyllithium
515 [486,487].
to be investigated_
followed
Other alkylations
by alkyl
Thus,
halides
were also
[487.488]_
reactions
leads
The use of epoxides
to ally1
alcohols
R’
R
instead
on compounds 514
sSi
nun, and lithium
in such
R’ /R’
OH
515 517 has been prepared
in the presence
LiA1(SiZ)4
R3
H
R’
514 alanate
substituted
halides
of alkyl
R “I ,-I-I
Finally,
afford
516 [489].
/ (i-C4Hg)2Al
of
(R-X) gave vinyl-
effected
where R = phenyl , butyl , and hydrogen to stereospecifically ethylenes
treatment
516
517
from chlorotrimethylsilane,
alumi-
of mercury [4901_
LITHIUM-HALOGEN EXCHANGE REACTIONS
9.
A variety derivatives [491]_
of o-haloarylimines
by n-butyllithium,
Hydrolysis
518 have been converted thencoupledto
of 519 gave dialdehydes
to their
519 by various
copper
o-lithio reagents
520_
R
518 Low temperature
‘sHllN
d 519
halogen-metal
exchanges
520
on isomeric
bromobenzoic
acids
and derivatives continued to be described in 1976. Thus, o-bromobenzoic acid wds converted to its dilithio salt 521 and condensed with ketones to afford
61
spiro
systems like
525 [495]
522 [492].
were similarly
Lithio
prepared
derivatives
523 [493],
524 [4?4],
and condensed with a varietv
and
of electro-
phiies.
522 R
521
523
c:i
ii 526 525 dibromo526 has been formed from the corresoonding
524 Cyclobutabenzyne bromoiodoaromatics
by treatment
trapped with furan or allowed present
in the reactions
and lithium certain
of
with n-butyllithium to dimerize.
diphenylarsenide
[497],
“Umpolung” reagents of the corresponding sation
for
with lithium
quinones
o-silylarylamines
like
gave derivatives
by reactidn and vinyl
of alkyllithiums bromides
treatment
Simple conden-
528
reagents [5013_
[SO33 have been prepared
by treatment
14991.
528.
527 Alkenyllithium
with
[498].
527 have been prepared
bromo compounds with n-butyllithium
with electrophiles
were also
diphenylphosphide
and were employed in condensations
to afford
and
Benzyne 526 was .
Genzyneintermediates
1,2-dibromobenzene
silyimethyldialkylamines
[496].
like
529 have been prepared
at low temperature Polyhalovinyllithiums
similarly
of 532 (R = aryl)
stereospeiifically
with vinyl like
by lithium-chlorine
with organolithiums
affords
iodides
[SOO]
530 [502,503]
and 531 In contrast,
exchange. lithium
arylacetylides
[5023.
R\
H
RA
Li 529
Other linsaturated included give
F
Cl
FH
ii
530 lithium reagents
533 which condenses
# Cb
in the synthesis
aldehydes
-F
R
-Li
FH
Cl 1 532
531 prepared
with carbonyl
c-methoxy-a.E-unsaturated
which is useful
F
by metai-halogen
exchange have
containing compcunds to ultimately (534) [504] , cyclooctatetraenyllithium
of bicycle-octatetraenyl
[SOS],
and various
lithium
acetylides
534‘made from l-haloacetylenes
and n-butyllithiun
[5D6].
OCH3 r./~~‘-__
---2
Li
Li 533
534
In the area of saturated converted
to benzyllithium
dibromide
to give
similarly_ lithium
halogen
compounds,
o-bromobenzyl
537 by n-butyllithium;
a bibenzyl
On the other
535
derivative
hand, o-bromobenzyl
536 couples o-Iodobenzyl
[507].
chloride
539 which has been condensed with a variety
Eromophenyl )ethyl lithium
bronide
536 is
with starting bromide behaves
538 is converted
to ary?-
of electrophiles.
bromide and y- (o-bromophenylIcthy1
chloride
also
-f-(0afford
arvl-
derivatives-
536
and trans.-iodotosylates
given
the corresponding
tally
[508].
an unrelated
Similar paper,
lithium
results certain
of dibromo orecursors
539
538
537
Treatment of cis-
reagents
klhich cyclize
were obtained rotanes
540 Gth
like
n-butyllithium
has
to 541 stereospecifi-
on the corresponding
542 have been prepared
4-enes.
In
by reaction
1ike 543 with ohenvll ithium f509].
\I:t
541
540 Finally, to carbenes
dichloro
derivatives
er
have been converted
Cl
XEOUCTIORS ADD RADICALADIOI15 A review article
asxnonia solutions tion
543
by methyllithium. Cl-,
lo_
542 544 [SlO] and 545 [Sll]
, D&a
dealing
and related
with reduction
of heterocyclic
reagents
arrived
to its
tetrahydro
too late
compounds by metal-
for
inclusion
in Sec.-
derivatives
546-548
in amnon-
t [512]. The reduction
of biphenyl
63
ia has been studied of 546.548 Possible
cis-
fected
of anthracene
and trans.-549.
yielded
Reduction dihydro
[514].
increased The latter
of fluorene 552
compounds arose
constitute
disilylated
For example,
short
Reductive
from metalation
amount
methylation
of
alcohol
a simple
synthesis
acid
periods
gave
tetrahydro
of fluorene
rea-
lithium,
mostly products
with lithium/-
and 9,9-dimethyl
of the 9-hydrogen
553 E ring of yohimbane 555 has been converted
of o-methoxybenzoic
benzene,
in ammonia for The small
an-
of silylatins
550 and 551.
554 and o-methyl-
by lithium/arrmonia/i-propyl reductions
corresponding
of i49 was ef-
in THF affords
[516]_
time.
bromide afforded
and sodium in THF has
Dehydrogenation
in the presence
[515].
by lithium
and 553
with increasing
552 The aromatic
the
afford
of benzene derivatives silylhydroaromatics
derivatives
ammonia/methyl
(556)
and 39% with magnesium.
in ether/benzene
respectively
i thium/TMEDA to
Qeduction
also
by lithium
and 1,3-dichlorotetramethyldisiloxane
ilar
The combined yields
the metal [513].
12.5:: with sodium,
were 18: with lithium,
by n-butyll
tracene. gents
of
mechanisms are discussed.
Reduction given
as a function
folloued
554 to a cyclohexanone
by aqueous acid
in the presence
of Z-alkylcyclohexenones
derivatives. atoms of the oarent
of alkyl
557 [518].
[517]. halides
Sim(9X)
64
H02C’
I .; OCH3 557
Improved 559,
procedures
respectively,
for
involving
the
conversion
the
use of
of
indole
ester
has been
ring opening,
and ring
reclosure
with liihium/aEzeonia/alcohols 563
used to remove the phenolic
from e’-tetrahydrocannabinol
been employed to reduce 3-furoic
aIS.
[522]_
The overall
to a butyryl
Reductive
boxyl
hydroxyl group pasked Lithiuc/azmonia has
[SO].
to 560 and 561 via E-elimination,
Thiophenes
to afford,
sequence
after
represents
like
562 have been treated
hydrolysis,
aninoketones
the transformation
like
of a thiophene
methylation
563
562
of 564 and its
gave 565 and 566, respectively group controlled
group was introduced group.
acid
[521].
561
try of the 9-carboxyl methy
pub-
group.
560
methy? iodide
558 and been
559
558 Lithiun/amonia
to have
H
H
as a phosphite
and carbazole
fithium/armonia/r!!ethanol
epimer by lithium [523].
that of methylation
from the side
in THF followed
Clearly,
of the molecule
by
the stereochemis-
at C-8 since opposite
the
the car-
C02H
‘CH3
Menthone (567)-isonenthone tively
to menthol
Other reducing
566
565
564 (568)
mixtures
(5G9) and neomenthol
media and hydrogen
(570)
including
systems studied,
in the presence
have been reduced stereoselec-
only
by lithium/ar;mocia
sodium and potassium
of ruthenium,
rhodium,
[524].
in various
and platinum,
were
not stereospecific.
iin +:-unsaturated duced
of
IO-epieudesmane
bromide to afford,
among other
from C-alkylation, of
like
ketones
and a tetrahydrofuran
intermedeo:
has been reductively
572 has been converted
the presence
an epoxide.
570
or lithium/ethylenediamine
sesquiterpenes
Methyl benzoate
ter
ketone,
by lithium/ammonia
propiophenone
569
568
567
have been re-
as part of the synthesis [525].
ethylated
by lithiun?ar;monia/ethyl
ethyl henzyl ether from 0-alkylation. products, and 571 from ring reduction [526]_ Ally1 es-
to allyllithium
to qive -i-alcohols
CH3Cil
reagent
573 by lithium
in THF in
r527]. _ Li+
‘\L ’
K’
‘\,
!
‘H
571 Tandem alkylation-reduction cyclopropyl sequence
aromatic
hydrocarbons
572 has now been applied [528].
The process
573 to the synthesis is illustrated
574 to 576. 0
OLi
574
575
576
of a-
by the
66 Related
to the above,
by lithium/amnonia the presence
cyclopropyl
phenyl ketone has been reduced
Subsequent
[529].
of amnonium chloride
reduction
to 577
of 577 by lithiumfamnonia
and sodium benzoate
affords
in
578 and 579,
re-
spectively. OH
OLi
I.
In contrast. [532]
cyclopropyl
are cleaved
the cyclopropyl
ring
The conversion
tion.
reduction
of
several
chloride
tions
the cis
530 [530,531] like
and 531
532 and 533, re-
several
organic
halides
to organolithiums
(and bromide)
other
products
534 was converted
in which
are presumed to have proceeded
tion
of 587 with n-butyllithium
tion
of configuration_
(587)
and heptenes
and trans hydrocarbons
reaction
with lithium
was not stereospecific
were obtained
via vinylic
[533].
[534].
in TtiF to since Such reduc-
radicals.
gave the respective
2
men-
586
585 reagents
deserves
to the lithium
536 via a cyclization
of E- and Z-4-chloro-3-heptenes
the vinyllithium of
products
yielded
then condensed with 525 to give
Reaction mixtures
to give
also
584 afford
in compounds like
has been opened.
Thus, allenyl
reagent,
rings
by lithium/ammonia
The latter
spectively.
579
57.3
577
In contrast, reacvinyllithiums with reten-
-‘\ 587
Lithium/awonia stead of the desired an electrochemical
reduction propellane process-
of 588 gave mostly 589 [535].
Similar
norbornane results
and a dimer inwere obtained
by
6i
589
588 ,+ChJoroenamines
590 have been converted
magnesium in solvents reaction
like
with deuterium
oxide
enanine 594 was observed
59G Various :Lnitrosamines
by lithium
bonds have been cleaved as illustrated r. --\
by radical
alkyl
ium instead
and ethyl
iodide
potassium
The C-alkylations than by nucleophilic
56
‘SH13
of adducts
afford
with alkyl
and the solvent
are said
halides [540].
598 and 599 (ortho
and cesium ketyls to occur
give
via initial
[gJq” 599
and para)
to all
to the use of
have been studied
600
Jith-
as-
the lithium
but no 600 or 601. of these products.
electron-transfer
)Af
to alkyllithiums from 597 and the
For example,
and para)
rise
displacement_ 0
(ortho
References p
i -\
converted
j.
$)-);I
(
L-I
ketyls
Carbonby Jithium/-
of 595 to 596 [538].
derived
cation
593 secondary
[5373.
contamination
of benzophenone
R2?r-\
in good yields
596 have been quantitatively
595 chlorides
of the alkali
In contrast,
)i-i/
[539]_ The success of the method is ascribed of sodium and to the steric bulk of 597_
Reactions a function
hR2
?,R ‘2
hydrocarbons
and
after
Deuterated
592, H=H 594, H = D to the corresponding
‘*-C6HJ3
anion 597 without
alkyllithiums
593.
and magnesium in ether
to give
by the conversion SeCH3 Xyl
‘L,’
Various
_(
>
591 have been cleaved
amines in very low yields
ketyl
were enamine 592 and diner
\.-iLi /; \ hR2
2
ethylamine
sodium,
The major products
with sodium and magnesium only. H
>;;;c:,
sefenium
to 591 by lithium,
THF and hexane [536].
steps
,;a 601
rather
Overreduction tyienic kali
ketones
metals
has now been avoided
like
in liquid to azo/-
of steroidal
naphthalenes
Lithium naphthalene
ammonia [541].
in a new synthesis
ployed
nitrobenzene
in the cvclization
602 to 603 by using alkali
of (?)-sempervirol
instead
has also
aceof al-
been em-
15421 and in the reduction
of
and__azoxybenzenes [543]. -./. .t>
_/-
-J1
_ ..I,+
t 111
, i .---
IA/
‘\ aH 603
602 ll_
REACTIONSWITH INORGANIC Several
like
AR0
I-cyanocarboranes
and m-carboranes
ORGANOMETALLIC
COMPOUNOS
have been prepared
with phenylcyanate
604 have been synthesized
[545].
of 606 with n-butyllithiom
by reacting
605 with certain
rivatives
papers appeared
carboranes
(8lOHl2)pdjphenan) 606
in 1976 describing
of germanium, tin, compounds [547]
the preparation
Carbanion
607 [547,548].
and lead to give and benzyl
and reactions
607 has been condensed
608 [547].
bromide [548],
Reactions
and of lithium
of de-
of 608 are discussed_
608
607 Other boron-containing methoxyboron chloride.
molecules
lithium,
prepared
and silicon
using
SiCMOCH3),14
into
the details dilithioalkanes
except of
[SSO].
610
611
metals,
layered
and Ta. X = 5, Se, and Te [551]. cases
n-butyllithium
and titanium
has been employed to
MX2 compounds where M = Ti, A limiting
VSe2 which gave Li2VSe2.
the preparation
and 610 from
CH3-0-CBIOHIOCLi
In the area of transition lithium
were 609 from di-
[549]
(Cii3-~-CB10H10C)3P
609
intercalate
lithium
tetrachloride
611 and bis(methyl-o-carboranyl)chlorophosphine
in all
lithium
605
bis(boryl)methide
607 with carbonyl
o-
complexes
606 has been made by treatment
(Ph3P)21r(CO)Cl
604
with derivatives
C-lithium
iridium(I)
in THF [546].
(Ph3P)21r(CO)(c-carb)
Two full
by condensing
New stable
[544].
An anion of phenanthroline-containing
of lithium
.i
composition A full
of titanium(IV) dichlorides
[f&G?].
Zr.
Hf. V, Nb,
of LiMX2 was obtained
paper appeared describing
metallocycloes.
like
The characterization
612 from and
69
reactions
of
prepared
the metallocycles
from alkyllithiums
dicyclopentadienylzirconium methylzirconium
(613)
Other compounds in this
is discussed. included
and hafnium dicarbonyls and zirconium(W)
[555],
[554],
614 [556].
*p3
lithium
pounds similarly lun [559],
prepared
I t-
1
CH3 -2
615 have been prepared
and niobium(V)chlor
include
hexacoordinated
_i
I
614
compounds like
cyclopentadienes
y3
! Zr (ii--fi+O
613
Cyclopentadienylniobium tuted
[553],
bis(fluorenyl)di-
amides like
(C13H9)2Zr(CH3)2
612
family
tetrakis(pentafluorophenyl).zirconium
from- substi-
[557,558]_
pentamethylniobium
[559],
tantalum complex 616 [560],
Other com-
pentamethyltanta-
and tetamesityl
com-
pounds 617 (M = V, Cr) [561,562]. ,CH3 (CH3-@&--+~Li 3 617
616 615 Carbene complex 618 has been synthesized reagents,
phenyllithium,
then trimethyloxonium
complex 619 has been prepared and lithium
cyclopentadiene
hexacarbonyl
, lithium
ium and tungsten species
like
/
--ArCr(C0)2(C
\
[564].
and triethyloxonium
621 have been condensed
action
fluotoborate
reagent
chromium
[565]_
Chrom-
with organ01 i thiums to give
0CH3
I Ph
/OCH3
.OCH
)
(CO)5Cr(C$Ph
(co)5w=/il \ Ph
3,
Ph 622 more papers appeared discussing
of molybdenum and tungsten Thus,
full
with molybdenum(II1) to afford
from
619
621 Several ple bonds.
Carbyne
and 623 [567]_
‘Ph
properties
[563].
tungsten-bromine
Compound 620 was prepared
618
(CO)$l(C
fluoroborate
from the corresponding
dithiane,
complexes
622 [566]
from ?-aryltricarbonylchromium
625 [569]
papers describe chloride
to give
and 626 [570].
of 626 with methyllithium
623 structure,
the preparation,
compounds comtaining the reactions 624 [568]
metal-metal
of lithium
yields
dial_kylamides
and with tungsten(IV)
Other examples are cited. 627 [571].
A related
and multichloride
In addition, condensation
reof
i0
anti-626 tion
with lithiomethyltrimethylsilane
of configuration
at tungsten
Mo2(NlMe2)6
U2(NMe2)6
has been shown to occur
via a bimolecular
four-center
with retenmechanism 15721.
(Et211-7%
H2C12(NEt2)4
CH3
Dihydrides the latter acid
reacts
chlorides,
627
626
625
624
to give tetramer 629; 628 (El = MO, H) react with n-butyllithium at the transition metal with alkyl halides, as a nucleophile esters,
and benzaldehyde
to afford
metal-carbon
systems
like
63D [5731_ n5-cp
n5 -cp
Y.M/H
3 -Cp’
?;_C/
H
’
‘5
((C5Hg12MHLi14
Other chemistry
in this
631 from hexamethyltungsten more fluorines phenyilithium
family
included
the preparation
and methyllithium
of 632 by organolithiums across
and tertiary
630
629
628
the azo linkage
[574],
[575],
of tungstate
the replacement
the stereospecific
of 633 [576],
and I-arylation
of
of ethers
PhHC16Li
633
632 Manganese compounds 635 fR = CH3, Ph), lithium
with 636, represent
carbene
is stabilized
complex (637)
carbene
as a ligand
has been obtained
/
complexes
634
prepared
by reaction
where a dialkyl-
to a metal atom [578]. similarly
MO calculations
C5H5(C0j2Re=C \
have been performed
that these
of nucleophilic reactions
at coordinated
on 638 and 639 to determine
attack
are frontier
rhenium
CH3
637
636
the site
of methylor arylalkyl-
An analogous
3 635
-
[579]_
C5H5(C0)2MnXR
C5H5(CO)2Mn=C
that attack
of one or
amines by 634 [577]_
631
.cluded
ion
addition
[CsH5Mo(C0)2?W]PF6
control
‘P .
on such species rather
CO is much more likely
[580].
factors
than charge controlled for the acyl
which
It is conspecies
and (639)
‘71 than for
the carbene
condensed Protonation cule
complex
(638).
Experimentally,
with 640 and 641 at CO to give of 643 afforded
the enol
642 [581]
methyllithium
has been
and 643 [SSZ],
respectively.
tautomer of a metalloacetylacetone
mole-
[582]. OCH3
/ (COJ5CrC
0 (CO)5F!n/K
“ii
(COj5Rn /Y
?
Ph
3
638
639
64’3
-_: (COj5Ze/-\ 642 The first thesized
acylsilane
derivative
of a transition
from 655 and triphenylsilyllithiun
metal,
644,
has been syn-
[583]_
; (C0)3jP)2ReN
(CO),Qe(P,)
‘SiPh3
644 Other rhenium and manganese compounds prepared dirhenate(III)
(646)
cctamethylrhenate(Yif and allenylidene
fron methyllithium
_
645 in 1976 include
and rhenium pentachloride
(64E) fro:n methyllithium
octamethylor 647 [5%].
and hexanethylrheniun
compound 649 from t-butyllithium
and acetylene
[535],
complex 650
[5863. Li2Xe2(CH,), JO
Li2Re(CH3)8
Re,(KPh),Cl2
646
648
647
649
650 * ferrate
Lithiuncycloheptatrienyltricarbony~ various
metal
carbonyl
halides
to aive
Mn, Re. X = 3 and 14 = Rh, X = 2)
verted
to bisffulvalene)diiron
ferrocenes prepared
[589]
[587]_
(654)
(651)
has been reacted
hetero4inetallic
complexes
Dilithiofulvalene
by iron(I1)
chloride
(653)
by treatment
of appropriate
lithium
has heen con-
[588].
and 1,1’,2,2’,0,4’-hexakistrimethylferrocene cyclopentadienes
with
652 (M =
[590] with
Polymethvlhave been iron
72
bromide and chloride,
respectively.
(C7H7)Fe(CO)3Li 652
651
653 654 Two related been prepared [591]
bis(cyclooctadiene)cobaltlithium
from 1,5-cyclooctadiene(cyclooctenyl)cobalt
and from cobaltocene Iridium
respectively. responding ophilic
iridium
nea protecting
and lithium
complexes
chloride
reactions
of
like
group for
and aryllithiuns
peptide
ethylene
[593].
syntheses
complexes
alkylphosphine,
657
with ;-MO-C bonding,
reaction
and ethylene
affords
illustrated
of this
same nickel
compounds like
reagent,
[Li(THF)4]C[Ph2P
dinitrogen-nickel
in ether
phenylsodium
nickel
[SSS].
di-
Xi(C2H4)2
/ \_
?iI (C2QZ1-
complex 660 has been prepared
phenyllithium.
by reaction
with phenyllithium/phenylsodium
Ethylenebis(phenyllithium)nickel
compound have been synthesized
reagent.
lithium
659
all-rrans-1.5.9-cyclododecatrienenickel nitrogen
have
TYEOA, and
659 [597].
658 “Side-on”
by 658, (RLi),
organolithiuns
[Li (2T?lEDA)]+[PhNi (C2H4)2]-
nucle-
for a
(CO)Ir(Ar)(PPh3)2
(C8H12)2CoLi(THF)x
Similarly,
[596].
Two papers described as model reactions
656 (0)
[592],
from the cnr-
[59$.595]_
from bis(cyclooctadienyl)nickel,
been prepared
of cyclooctadiene
657 have been synthesized
655 nickel
and phenyllithiun
in the oresence
lithium-cobalt-phthalocyanines
(C,H12)2CoLi(LiPh)-2(C2H5)20
hovel
compounds 655 and 656 have
phenylsodium.
and the
by reaction
of
and ethylene
of
and
related
the same triene-
[599].
660 Other compounds in this bony1 dianions
like
family
661 by reduction
recently
described
of platinum
include
chloride
platinum
car-
systems or pre-
'73
formed platinum
carbonyl
from the corresponding kel chloride
systems by lithium chlorides
from a complexed
and metallocycles
[602],
nickel(II)
like
[600],
platinum
complexes
and perfluorophenyllithiun chloride
[61)1],
and lithium
663 from the platinum
chloride
like
662
benzylnic-
tribenzyltin and 1,4-dilithio-
butane [603] _ Pt3(CO)6Li2
A variety
of
thorium derivatives
664 (R = alkyl
pared by reaction
of the thorium chloride
Grignard
[604].
reagents
663
662
661
Ring-bridged
and alkenyl)
derivative
have been pre-
with organolithiums
uranium halides
and
665 have similarly
CG(C5H4)212U2C15Li (THF12
(qs-C5Hs)3ThR
aJGbJ Lit
665
664
666
Li+
Terbium and holnium compounds 667 (R = t-C4H9) have been synthesized the reaction prepared
of 668 and lithium
by the interaction
di-t-butylphosphide
[606].
of 670 with n-butyllithium Ln(=>?<
667
663
The first
organogold(I)
pared by reaction
complex containin
of perfluorophenyllithiua
tetrasilane
673 may be prepared
I,Cl3
670 a S-donor.
671.
has been pre-
and 672 [6g!?].
metal.
Table,
by treatment
[609].
This same paper describes
with lithium
P’,
672
tetrachloroplatinate
sink.
Ln[-
ClAuSC4Ha
Turning to Group IV of the Periodic
lithium
from
669 has been
[607]_
669
671
potassium
Ylide
)3
(C6F5)A~SC4H3
cyclopentasilane
been
of 666 (G = Cti2, Si Z, n-propyl ) wi.th uraniun( IV) chloride
made by condensation [605] _
The latter cleavage
it has been found that perarylof either reagent reactions
674 or 675 with is said
to act as a
of perarylcyclo-
p\siPh Ph\
--,*ilPh
_‘-
p/-S’i
I
\Pil
‘+Ph Ph
ph5si?h
674
673
Other preparations
of cyclic
silicon-containing
by 676 from 1,8_dilithionaphthalene 6T8 and disilane
ylide
conpoun-!s
are
and dialkyldichlorosilanes
679 16111,
illustrated
[610],
677 fron
and 680 from 681 and dic5lorodinethylsilane
[6121_
(CH3)3P
(CH3)3P
676
677
678
680
681
CH 13 Cl,Si\
; C12Si/
1
CH 3 679 Divalent or,
species
682 (M = Ge. Sn. Pb) have been prepared
from 683 and 684,
s*hen X = Sn or Pb, from 683 and MC12 [613,6147. ZS-
Fi
Sir
ZSi
,Siz J--+l-_(;
‘>-( ZSi
‘\
> _Sl
Sis
682
683
Imidazolidinonederivative aprotic
solvent
reactions
metal to give
that 685 lies
684
685 has been tested
for organometallic
with ketones and lithium It is concluded
‘Sis
for
by reacting
disilyated
its
suitability
as an
chlorotrimethylsilane
derivatives
like
between THF and HVPA in promoting
686 [615].
such reactions.
i5
Other chemistry reagents
the preparation
in this
across
L-6171, the synthesis chloride
group included
the addition
of of
tin
triphenylsilyllithium
lithium
using get-manium(!:‘)
of organolithiums
linkag..e of :-germyl
the nitrile
of 683 from the correspoxding
and the conversion
‘*i_
686
685
Grignard
/Xii:
0
-CH3
nitriles
reagent
and
687 [616],
by trans.-netalation
from 689 and methyllithium
cyclopentadiene
[618],
to cyclopentadienylget-manium
tri-
chloride [619]_ :Si
3EeCH2CC
(C2H5)
like
(CO)4CoSiPh3 l-i
687
688
An interesting derivative fected
691 and dichlorodimethylsilane
using
SilSiCl3
689
690 has been obtained
dispirotetrasilazane
The synthesis
[629].
and n-butyllithium
from tetralithio
followed
by addition
of 691 was efof aniline,
then
more n-butyllithium.
691
690
Treatment of silicon-nitrogen cyclic afforded 622]_ yielded
systems_
693a-b apparently In contrast,
694 presumably metalation
to be prepared
Rcferemesp.58
R’
= Ph)
via methanide migration
692c (R = i-C-&.
695 with n-butyllithium similar
systems 692a-c
Thus. 692a (R = t-C,H,.
via a silicenium
and 692b
ion [622].
gave 696 via the latter
(R = R’
to a silicenium
R’ = Ph) with the
of 697 gave only N-lithiation,
[624].
with n-butyllithiun
smaller
Reaction
route
[623].
the first
also
gave
= t-C4Hg)
ylide
i-propyl
of silyl On the
[621, grouo
system oth
hand,
such organometallic
76
t-c&,
Y
:
Si-R’
I
I
X--
Zi-N-:i-NHt-C4Hg
; Si-
I= 692a
R’=Ph)
(R=t-C4H9.
692b
(R=R’=t-C4H9)
692~
(R=i-C3H7.
i-C3H7\
p3 N-
IiHt-C4H9 YPh
I
i
TSiL
N-t-C4Hg
694
693a
(R’=Ph)
693b
(R’=t-C4H9)
R’=Ph)
(t-C4H9)2Si,
AF NHt-C4H9
Azosilolines
like
and phenyllithium
697
696
695
698 have
been
synthesized
from
J.
Silylated ate
ter
aldimines
complexes
enamino-tin yields
chlorotributyltin
halides
may now be simply
[626,627] system,
previoulsy 16291.
Zi-N=CHR
with for
described Similarly,
prepared
by treatment
chlorotrimethyl_silane
example,
702-703,
by treating metalloimines
[628].
of The
can be obtained
iminolithium 704 have
in
reagents
bet-
with
been obtained
M+(C2HS)3B-N=CHR
from jR \
CH3--=-N
702
701
Ph
Lit
-YNR 703
new imino-
[6301.
700
SnR3
699
699 (700)
701
metalotropic than
705 and metal
precursors
_Ai_ _/’ - NHR
698
boron
benzyne
[625].
Ph
Ph 704
705
SnR’3
ii Nitrogen-nitrogen with lithium
and Group IV systems.
tetrachloride, reaction
and nitrogen-oxygen
and butyllithium
Thus, reaction
affords
708 L-632]_
have been synthesized Finally,
Several
bis(trimethylsilyl)hydroxylamines n-butyllithium,
(Si)
NOSiz
lithium
phosphinelithium like
like
followed
708 / PhN 1.
OSis
Sir
711
712 have been prepared
by addition
of
by reduction
chlorotrimethylsilane
compound 713 has been synthesized
n-butyllithium
from
[634].
710
Organosilylphosphines
709
[633].
have been prepared
ZiNHOSiz
709
with
(711)
gives
like
and chlorosilanes
707
2
Similar
then hexachloroethane
and chlorotrimethlsilane
706
carbon
707 [631].
tris(organosilyl)hydroxylamines
from 710, n-butyllithium,
phenylhydroxylanine,
been combined
of 706 (M = Si),
aminoisocyanide
of 706 (M = Ge) with an organolithium,
germyldiimine
phines
systems have also
of phos[635].
Silyl-
from 714 and organolithiums
[636].
(Zii)3P
Calculations complexes states these
have been performed
[637] _ The authors
on the activation
conclude
in which the N-N bond is highly states
can be described-as
of nitrogen
in n-iinN
that stabilization
of the electronic
loosened
and that certain
occurring
can occur
from one- or two-electron
of
reduction
of nitrogen_ Diazadiphosphetidines phenyllithium
traphenylphosphonium dialkylamides, or the formation group.
like
715 have been prepared
Phosphineimines
[638].
chloride
though,
affords
like
and lithium
alkylamides
homolytic
decomposition
of N.N-dial kylanil ines,
by treatment
717 have been synthesized
depending
[639].
from te-
The use of lithium
of phosphorus
on the size
of 716 with
compounds
of the alkyl
R
I
CH RH’ 3
P
PC” ‘CT
‘I/--
R Ph P=iiR 3
I
CH3
Lithium diphenylphosphide chloroethenes ethylenes.
to give
depending using
and arsenide
stereospecifically upon the central
phosphinoarsinoethylenes prepared
are also
lithium
chemistry
and chlorodialkylphosphines 720 and organolithiums
mono- or diphosphino-
rivatives
and arsino[640]. %xed compounds
Other Group V and VI
have include
[641 J, sulfur
and Grignard
with 1,2-di-
atom and the stoichiometrv 718 from lithium
cyclopentadienes
compounds 719 from suliurdiimines
reagents
[642],
[643],
722 from nethylalkoxychlorosilanes
?-silylcarbanions
have been condensed
described_
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717
716
715
721 from
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[645]_
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[644],
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724 with a py-
ranose bromide [646] _ Rn=S-R
I
R’ 718
AH
W=S=NR
(CF3)2S=:lLi
720
721
‘R
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R’ I
R”
RSeXSiRY’
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12.
724
723
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(1976) 6521, 604.
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605.
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H.
Schumann and 5,
608.
R. Uson. A_ Laguna, (1976) 353.
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Yang and H.
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612.
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and J.
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and F_ Kando.
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426
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(1976)
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and R. Corriu.
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J.
Sot..
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127.
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626.
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Gotz,
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Chem. Cl?.
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7.
LITHIUM At:l’iUAL SURVEY CO’IERIKG THE YEAR I976
EDWINM. WISER
Department of Chemistry, Missouri 65201 (U.S.A.)
University
of Xissouri-Columbia,
Columbia,
COF:TE:!TS I 2
Reviews and Books Structure and Bonding Studies Kinetics and Mechanism 3. 4_ Metalations A. At sp3 Carbon 6. At sp2 and sp Carbon and at Nitrogen Lithium Carbenoids and Other Halogen-Substituted Organolithiums 65: Addition and Substitution Reactions 7. Heterocycles Copper-Lithium Reagents and Other “Ate” Complexes 8. Lithium-Halogen Exchange Reactions 1:: Reductions and Radical Anions 11. Reactions with Inorganic and Orqanometallic Compounds 12. References 1. 2.
1.
:: 21 31 35 37 43 5% :: 68 78
REYIEWSAND ROOKS Reviews and chapters
lithium
chemistry
in books devoted
included
- 13C XMRof organolithium - Fast reaction
studies
- Use of lithium tron-transfer thesis
process
- Annulation - Syntheses - Preparation
(1977)
or in part
to organo-
[1,2]. in solution
addition
reactions
c31. as models for an elec-
[4]. in the use of organolithium
reagents
in organic
syn-
preparation
and synthetic
uses of
ketone enolates
[6]_
[7]. of caretenoids of alkenes
[8,9]. from tosylhydrazones
Annual Survey covering l-131_
wholly
[S].
- Regiospecific
Lithium.
reagents
of carbanions
organocuprate
- Recent developments
either
the following:
the year
[lo].
1975 see J.Organometal.Chem.,
130’
2
Recent methods forthe
synthesis
of polyfluoroaromatic
Preparation
and chemistry
of unsaturated
Nucleophilic
substitutions
at acetylenic
- effects
Allopolarization tiona?
anions
carbon
of substituents
acylation
[13].
on the reactions
reagents
Metal-ammonia reduction compounds [18].
and related
reactions
solvents
in organic
synthesis
Boranes and heteroboranes
[23]_
Metalloborane
with ligand-metal
derivatives
metals
plexes
in organic
synthesis
single
bonds [24].
[25].
nucleophilic
aromatic
substitution
metals
[26].
in :-arene-metal
com-
[28].
Transition
metal dialkylamides
- Gold chemistry
organometallics
metal derivatives
- Preparation
and disilylamides
[29,30].
[31]_
- o-Bonded actinide - Alkali
carbonyl
[19,20,21,22].
c-Alkyl and -aryl complexes of group 4-7 transition Metal-carbene complexes in organic synthesis [27]. Metal assisted
[17].
of =,%unsaturated
_
complexes
Transition
of ambifunc-
[15].
utility of P-oxazolines [16]. of alkali metals in ammonia and other
Boron “ate”
compounds [ll].
[12].
[14]-
Nucleophilic Synthetic Solutions
lactones
of chiral
of tin
[32.33,34-j. [35].
trioganotin
halides
using
organolithium
reagents
[361- Preparation - Inorganic and other 2_
of new homoleptic five-membered hetero
elements
and amides [37,38].
systems consisting
X-ray diffraction
nitrogen,
[39].
has been employed to determine
of dilithiated
(TMEDA) (Fig_
stilbene
the hydrocarbon
to one another.
The lithium
portion
atoms chelated
above and below the midpoint
bene molecule.
The stilbene
~-delocalized other
carbanion
than disolvated
and crystal
bis(lithium
2) [40].
PMDTA)structure atoms_
rinss
by the amines are located
of the olefinic
complex to be isolated lithium
(PMDTA) (Fig.
is planar with the aromatic
equal distances
contains
the molecular
complexed with tetramethylethylenediamine
1) and with pentamethyldiethylenetriamine
In each structure,
first
of silicon,
STRUCTURE AND BONDINGSTUDIES
structures
trans
alkyls
ring
at
bond of the stilis said
to be the
and so characterized
which
Solution
X-ray scattering
have been used to determine diethyl
ether
distance
solution
is estimated
most probably
as structure
the authors
of 1 with methyl iodide, and accounts
reactions.
paper,
In another
in dimethyl
for
its
I Li
I Li
I
I
I
that
LiCu2(CH3)3 (2),
ether of LiCu(CH3)2,
I Li
the dimeric
struc-
in Corey-Posner to show the ore-
and Li2Cu(CH3)3
(3)
[42].
3
CH3-Cu-CH3-Cu-CH3
CH3-CL.-CH3
A la;-ge number of other study organolithium
publications
First,
reagents.
of R- and racemic
structure
The copper-copper
unusual reactivity
I_
fine
1 [41]-
and ‘H h?tR as a dimer in
‘H NMRhas been employed at -136”
CH3-Cu-CH3-Cu-CH3
spectra
exists
conclude
CH3-Cu-CH3
i’
depression,
dimethylcuprate
fi and the methyl groups are either equivalent Based on kinetic studies on the exchange even at -60”.
ture of 1 is important sence
vapor pressure
to 4.420.7
or undergo very rapid reaction
methods, that lithium
also
line
shape analysis
2-methylbutyllithium
as a result
of chemical
described
shifts
‘H !iHR to
the use of
in 300 FTHz‘H NFlR
hexamers in pentane has revealed among diastereomeric
aggregates
The spectra of the racemic reagent indicated 1) an inversion at carbon c433. bonded to lithium which occurs within a hexamer aggregate and 2) an interaggregational
exchange
of organolithiuas
In constrast,
the R-lithium
the inversion
process.
processes
reagent
showed a line
The heats and entropies
inequivalent
sites.
shape chanqe ascribed
of activation
for
only
to
the two
are listed.
The unstable by metalation as evidenced
lithio-Z,E-1,3-diphenylallyl
by XMRspectroscopy
and the following tl,2(-30°)
values
on its
are recorded:
The later
in similar
(4-Z,E)
and by reduction
of
perdeuteratedphenyl
of 4-Z,E to the more stable
= 2-g min. 4-Z,E
anion
of cis-1.3-diphenylpropene
rate of isomerization
observe
between magnetically
5 by lithium derivative.
4-E,E was followed
tit* = 17.321.8
value explains
has been obtained
kcal/mol.
why previous
The by RR.9
~55. = 2.028
workers
failed
studies.
r
Li+
7
bh
. I!3
4-Z-E
A ;
H\&+/Ph
H
Ph
Ph
H
5
metal
4-E,E
e-u.,
to
Several studied
9-aryi
by both
magnitude of ring bered ring tuents
[45].
9ave linear
nhich
ho;;roaronatic
based on SIR alone
Metalation annulenyl
theory
conclud?
that a ring
that paratrclisn magnetic
results
dipo?e
that one might conclude compound [46]_
without
a caveat also
Since
is issued
considering
cur-
of the ‘:.M-LUYO energy oao. frop
low-l:/ing
transitions.
a suffi-
that 7 is a completely
earlier against
stabili:ies
work had demonstrated reaching relative
such conclusions to an aopro-
compound_
7 of hydrocarbon systei
data _ This anion ion e;:hibiting
of the eight-men-
P
the authors
is a function
8 9 by c-butyllithiun
11, whose ‘H iMR was compared to that of [13]
shifts
(6) were
groups on the
of the ‘i! WR spectrum of 7 with that of 9 reveals
number of similarities
reference
the chemical
through allowed
that 7 is not homoaromatic, priate
styrenes,
the current
accessible
A comparison delocal iced,
Since
anions
of such aryl
with the tr values of the phenyl substiP the trend of >max values relative to ? !r opposite to that
support
states
the effect
plots
is being observed
These results
cient
of methylenecyclooctatrienyl
with para-substituted
rent effect excited
currents
protons
and since
observed
derivatives
‘H M+iRand UV to test
cs7j.
12, a peripheral
It is concluded
is apparently
anti-aromatic
the first
properties.
has given an anion.
that
structure
perturbed 10 best
example of a perturbed
10 or
arorr.a:ic fits
annulenyl
the
an-
n-butyllithium
A novel
by ‘H NMRto involve spectra
were obtained
rearrangement
of 13 to 14 has been shown
the intermediacy
of carbanions
15 and 16 [48].
for
The latter
of 17 to 18. preparation
catalyzed
the corresponding represents
intermediates
a new and very convenient
of the 4,8-dihydrodibenzo[cd,gh]pentalene
sulfur-containing
10-a electron
for
the
15
18
17
16 Two cyclic
route
system.
14
13
Similar
in the conversion
anionic
systems have been studied
In the first
case,
19 gave 20, the ‘H NMRof which led the authors
to speculate
the presence
planar,
Secondly,
by NMRto determine
the extent
10 n-aromatic
delocalized
ture of 2i and 22 afforded is delocalized
into
of aromaticity. system [49].
23 whose ‘H and 13C HMRsuggest
the thiophene
ring of this
/\ 0 f3+3-CH3
molecule
0 -
of a mix-
that negative
charge
Li*
20
(WLH3)- Li+
a,,, 22
23
of
of a
[50].
0
19
21
metalation
metalation
i Evidence data for ides
has now been provided
the previously
(24)
and alkali
inferred
dipivaloylmethides
vided data as a function ample,
the greatest
lithium
cation
cation.
In
E.Z-
(26)
kali
cation
by ‘H NMR, far
ion-pair
[52,53]_
alkali
is lithium
sities
of the signals
cator”
in the titration
solvent.
and the E,Z-isomer from
shift
of the cation. was produced
was effected
pro-
For exby the
by the cesium
in methanol as a function
acetylacetonates
In this
cation
dibenzoylmeth-
Each of the techniques
‘H XHR has been employed to study the amounts of
papers,
(27)
[51]_
charge density
downfield
and conductance
of alkali
in the ‘H RNR spectra
shift
the smallest
tWo other
and Z.Z-
(25)
of the positive
downfield
while
infrared,
structures
both
chelation (26)
is unimportant
predominates.
conformations
have
of sodioacetylacetone
except
cji al-
when the
The integrated
inten-
been employed as an “indi-
with lithium
salts
H
H
H
24, R = Ph
26
27
[53].
25, R = I-C4Hg_ Radical
intermediates
dichloromethanes
(aryl
by ‘II and “F
studied
Such effects arylmethyl
in the reactions
chemically
were observed and butyl
of diarylchloromethanes
= phenyl and pentafiuorophenyl) induced
nuclear
on 28 and 29 arising
radicals
polarization from in-cage
and recombinations
and aryl-
with n-butyllithiun effects
were
[54]_
recombination
of arylmethyl
radicals.
of re-
spectively.
,!r(Cl)
tively
example of diastereotopic
charged
silyllithium
silicon
[55].
the nonequivalence of 185”_
A barrier
Metalation ‘H,
atom has been observed
of the diastereotopic
nega-
in the case of diisopropylphenylof this
comoound revealed
methyl groups even up to temperatures
about silicon
of two phosphonate
13C, and 31 P NMRspectroscopy
metalating I-butoxide
groups caused by a tricoordinate
Thus, the ‘H 270 MHz NMR spectra to inversion
I
Ar(C1) 29
28 The first
CHAr
ArCH-
AriHC4Hq Ar(C1)
esters to afford
of >24 kcal/mol
is suggested.
(30,
R = H or CH3) has been shown by eithe. r 31 or 32 depending upon the
Thus, while E-butyllithium affords only 31, lithiumagent [56]. and potassium t-butoxide gives both 31 and 32; the latter species
S
predominates
with potassium
cation_
CH3CH20,
CH3CH20 \ , CH3CH20
[
CH3CH2dp%-+C\.OCH 0
5-
CH3C”20’r2CH3 O-_iiO*
3
6
R 31
30
1
Finally,
H NMR, infrared,
33 and corresponding and the related tion
CH3CH20,
:I
q--iHC02CH3
sulfur
arsenic
of silylethers,
32
and Raman data have been published
and selenium
derivatives
phosphines,
derivatives,
and for
These species
[57].
for
lithium
alkoxide salt
were prepared
34
by reac-
and arsines.
H3SiOLi 34
33
tra of
were its
obtained
dianion
from
tetraphenylethytene Lipfield
[58].
Tines for
of the dianion
both the dilithio
ions are also
of alkali
of the metal,
and the cation
size,
the hv-
than is the latter
one.
gave
as only one other
midway
are rapidly
Ultraviolet
spectra
exchanged of the dian-
The authors
[SS].
between the contact
the
u-carbon
of the enolates
alkali
metal salts
of several
and others
chemical
with
enol
compared to the reference
density
at the a-carbon
shift
where shield-
of the ion pairs
[60]_
derived
and the
same carbon
ethers
shifts
as the
to be spread more evenly
the chemical
metal enolates the
the exis-
chemical
shifts
of lithium
is emphasized_
have been obtained
compared
and trimethylsilyl
charge
The danger of comparing
n-system.
atoms
the negative
discuss
ion alpha-carbon
dependency on these
causing
by ’ 3C NMRas a func-
has been studied
and temperature
the solvent
The 13C NMRspectra
r-electron
as well
salts
t%e lithium
and sodium cations
that cations
reactions.
diphenylmethanes
dependence
to those of other
acetates
is suggestive
solvent,
is decreased
cyclohexanones, late
both lithium salts
ppm for
compound confirms
in the order methyl-THFz-THFXiME, and solvation
temperature throughout
and disodio
ppm and 43.42
to the dianion
containing
and intramolecular
tence of a linear
salts
dilithio
such spec-
Thus,
reported.
Solvation
ing occurs
52.66
is closer
and disodio
betr-reen the above two lines by both inter-
and the
of
compared to the parent
that the former cation
That solutions
tion
shifts
respectively,
and sodium salts, pothesis
to ’ 3C IiMRof organ01 ithiums.
papers were devoted
Several
from acetophenone,
chemical
atoms
of
The difference
the
shift
of
in chemical
compounds seems to be related
and is a function
of
the
corresponding
the cation
enoenol
shift to the
(K*>Na+>Li+),
9
the
solvent
(DME>THF>etherf,
and added
Tigands
Tike
HYPA and certain
crown
ethers. A l3 C WR port
the
of
several
coupling
were found to be higher ascribed
coupling
-t-lithiosulfoxides
such carbanions
that
Thus, the 1J(13C-H)
[611fones sult
study
theory
is in the opposite
pounds methyllithium
and cethane
reagent
in radicals
butene
is discussed
not be understood radical
of
18-crown-6 ducts
ether
The authors
adequately
without
ketyl
of
thienyl
[65],
were also
sui-
with the model com-
constant
is
smaller
in the
1,3-carbon-carbon
interactions
cyclobutene,
that “spin
conclude
recognition
of
is not necessarily
these
on spin
and trans-2-
densities
simply can That
interactions.” than such anion
greater
soio
is discussed_ for
phenalene
35 [53],
phenyiazulene
2.2,6,6-tetrarzethy’cyclohexanone and thiazoyl
five
of phenylacetylene
troscopy
of
[62].
have been reported
various
and
sulfur compounds, a reThis increase in the
realized
the coupling
SUD-
position
lithiosulfoxides
state.
direction
uhere
the
in the parent
from benzocyclobutenes.
to 8-hydrogens
the lithium
ketyls
derived
hyperconjugation
ESR spectra [63],
of
does not
even in a benzylic
than in the hydrocarbon.
In the area of ESR, the effect density
:ransmissions
constants
than those
to a change in the hybridization
constant
organolithium
cation
and sulfones
are pyramidal
ketones
arylphospine
1673.
including
derivatives
In the latter
employed to demonstrate
[6a].
and alkali
infrared
36 rwtal
of dihenzo-
the affect
f66],
case,
alkali
metal ad-
and optical
spec-
the reduced nature of such species.
4 0
36
35 Spectroscopic
studies
to be investigated. rivatives
of
Thus.
nitromethane
using the
techniques
infrared
other
in the C-H stretching -1 are ascribed
m31- Bands at 3040 and 3170 an
with a sp2 hybridized carbon atom. The infrared spectra of several bonylates
were obtained
ment [69].
The data.
provided contact
information and solvent
to indicate in connection
than ::MR and ESR continue
and Raman spectra
alkali
region
of
alkali
metal derivatives
formulation of manganese caranion environ-
and conductivity
experiments,
about the nature of bonding and complexation separated
ion pairs
as well
as in
de-
have been investigated
to the aci-nitro
the nature of the carbonyl with kinetic
metal
free
ions
phenomena in of
several
10
study.* resolution
species.
In an unrelated
rections
of the transition
obtained
by the use of absorption
Ultraviolet
spectroscopy
brium constants lenide, anions
causing
by.the
an increase
The ion pair
and the di-
at 860-560
have been
nm [70].
and ESR have been employed to measure the equili-
tetracenide,
are favored
structure
lithiotetracyanoquinidometiiane
spectroscopy
of the disproportionation
anthracenide,
reactions
moments of
of vibronic
of the ion pairs
perylenide.
interaction
of
the cations
in the coulombic
propagation
with the aid of UV spectroscopy
actions
[72]_
Three types of anionic
Iithium
in ether
naphtha[71]_
The
with the resultinn
di-
energy.
in the polymerization
studied
of
and pyrenide
of
to check for centers
isoprene
in THF has been
the occurrence
are observed
of side-re-
at 287 MI, 305 nm,
and 335 run. two of which may be due to 37 and 38. Li+ -CH2-CH\~-+CR2 ZH3 38
37 in this
Other papers of interest arylthiolate
anions
the ion pairing (ethylene
using
alkali
visible
1751, and determination desorption
studied
mass spectrometry
with methyllithium values
l-727,
2.025;
C-H bond length
1.078.
1.0623
to 1.1185
(if said
tetrahedral
mostly
from the lithium bond is suggested
-46.9596, -46.4203.
calculated
to be -185.4886
to -185.8611
total -53.744
energies [78],
(8):
-39.318
The total
described
papers were employed,
2_021:1_q69. 104.2”;
to -39.401,
(Hb), total -46.419
Monomeric methyllithium
[79]. (&:
hartrees
of the C-Li barrier
[Sl].
species
Clusters
ranges
tetramer
Li-Li:2.369-2.68;
energy of this
is
transferred
Methyllithium
Li-Cr has been
containing
[Sl].
of methylenedilithium
-53.131
by
[76]_
(Ha) and 1.068 105A”,
and the inversion
as follows
[Sl].
spectra
sets
The bond separationenergy
upon bond angles
as having bond lengths
Similarly,
five
bonding with about 0.8 electrons [78]
[73],
of carbanions
attachment
1.090
of
of poly-
substances
reagents,
1.122,
planar),
kcal/mol
are also
cation
C-Li bond length
l-089,
C-H: 0.95-1.095
be (hartrees)
lithium
upon angle);&H:
2.25-2.31;
ten atoms of lithium
formation
Depending upon the basis
to the methyl [77]_ to be -5.6
spectroscopy
of non-volatile
-46.7767,
of ionic
ion pairing
and fluorescence
on organolithium
(ii):
(if
from O-4 to 20.31 depending is described
using
(depending
) , -46.247
to consist
weights
have been described:
energy (har Zrees) : -47.0206,
ion pair
[74].
[77-al].
the following
by optical
by absorption
of molecular
In the area of calculations concerned
a study of
metal compounds in the presence
spectra
of xanthene and thioxanthene field
include
in THF and DMFdetermined
of fluorenyl
oxide)
area
(cis,tetrahedral)
have been calculated [80],
-53.074
to
to -53.030
11 (trans.
planar)
[SO].
wise described 1.208 i;
C-H bond length:
charge distribution calculations, state
and -53-7165
by the following:
1.056 w [77].
in this
of 39 rather
are discussed
[SZ].
Lithioacetylene
Another paper discusses
than 40 [84].
including
A wide variety
I-fiuoro-i-lithiocyclopropane,
42. and others
Li C
C--
Li-CsC-Li
40
Using ST0/3S atomic (43)
of solvent
lithium
A calculated E86].
time scale, = solvent cussed. suggested C871-
computations
structures
l-l-di-
below [S’i].
H
soecies,
computations
of pentadienyllithium
a bridged
lithium
CT and C5 have previously structure
dimethyl In another that
were performed
on both the co-
[SS].
In an attempt were also
it is concluded to determine
oerformed
the
on all:Jl-
to two trater noiecules.
structure
this
42
of allyl!ithium
than 43 by 6 kcaI/moI.
which contains
Since
(44)
on this
coordinated
proposed
41 and its described
41
orbitals,
and ion pair
that 44 is more stable affect
ethyl-
1-3-dilithiooro-
H Li
39
valent
orqano-
[77],
6, + 1; --;---(
Li
usino ground
of other
and vinyllitilium
and LiCH2X where X = LSeH, XH2, OH, F, and 9H2 1781, pane, difluorodilithiomethane. tri- and tetralithiomethane. salt,
the electronic
bridged
lithium
lithio
like-
paper or-edicts,
has a’double
ethyllithium
is
1.931 .t; C-C bond length:
compound 1833 Nhile a third
that monomeric dilithioacetylene
structure
lithiums
to -53_7851
C-Li bond length:
ether.
is said
the lithium
interacting
ether)
by both :-
has been
and z- bonds
been shown to be equivalent
to be equilibrating
The affect
paper dealing
bis(dimethy1
on the F!YR
as shown (45)
where 5
of methyl groups on such anions
with cyclopentadien:rllithium,
atom is most stable
it
is dis-
has been
above the middle of-Ehe
rino
12
Other ring [80.88],
clopropenyl tion
systems similarly
anions
[go],
anions
aromatic
and antiaromatic
dianions
[88].
Two papers discussed Both agree
the orbital
containing
stable
have included cyclopropane
4-,
‘;-,
certain
b-,
7-,
of 3-oxypair
atom rather
[91],
[89],
reac-
anions
and 1-thiocarbanions
are stabilized
[92.
bonding.
Such sta-
is conformationally
than conformer
dependent where conformer 46 ( w or e) is more are oroSimilar nc-siH overlap integrals 47 (y or a)_ It is suggested
the C-H bond antiperiplanar
to the lone pair of electrons
is much less
acidic
than that
in its
H. “<-.
that
precursors.
on the -:t-heteroaton,
H H
/
C
in such carbanion
gauche rotarner.
H
d_.
Q Y X
‘.
\‘C
;
B
46
\
47
ii
An -ab initio study has been performed on nitromethane. its aci-nitro and its conjugate base 49 [94]. The anion is best described
tomer [48],
but has an extremely
The total parent:
and
by overlap of and a .G* anti-
of the carbanion
than by (d - p),
posed for e-oxycarbanions_
planar
cy-
and other
and g-membered ring
alpha to sulfur
the lone electron
on the sulfur
anion
the electrocyclic
ant! butadiene
8-,
aspects
lithiocyclopropane
radical
[80],
of cyclobutene
that carbanions
bonding orbital bilization
[80],
3,3-dilithiocyclopropene
between the radical
931.
studied
I-l-dilithiocyclopropane
energies -243.2630;
CH2=rI
shallow
(hartrees)
for
48: -243.2532;
potential
49:
to pyramidal
using an extended
inversion_
basis
set are
-242.6573. 0
r”
-
H.$..
\ OH
+// \
o-
H#=N
a 0-
48
+i’ I
0
_
49
Other Papers discussing
mdlecular
with the SRy 1 mechanism of aromatic anomethide’C961,
curve
the species
tauas
and the structure
orbital
calculations
substitution
of the lithium
[95],
have been concerned
the structure
of tricy-
adduct of nethylenephospho-
rane [97]_ 3_
KINETICS AMI MECHANISM Several
to test cesses
if
:ypeS of ketones have been condensed with lithium dimethylcuprate the nature of the products could determine if electron transfer pro-
had occurred
to afford
radical
anion
intermediates
C98.991.
Thus, aryl
13
alkyl
ketones
tions.
50 with this
Though ketyls
detected_
Similar
attack
than to an electron was observed of
cuprate
products
transfer
process.
no products
ketyls
arising
from 51 were
of certain
ketones
52 gave
on the cyclopropyl
On t.he other
ketone 57.
diary1
ring
transfer
54 to ketone 55 and
In another
ketones
were rather
hand, such electron
and bromoketones
enone 56 to E.-f-unsaturated
affords
from 1.2-addi-
53; horrever, such products
reagent
of acetoxy-
that the reaction
arising
with cyclopropyl like
by the copper
in the conversion
Z-cyclopropyl
is disclosed
of the cuprate
ring-opened
to direct
gave methyl carbinols
may have been present,
reaction
some of the desired ascribed
cuprate
paper.
with lithium
it
dirrethvl-
[loo].
0
R’
53
52
51
50
R
0
R
0
0-
I
54 The electron been studied [lOi]_
transfer
as a function
efficiency
of g-methoxyfluorenide
in methanol has
of the nature and concentration
It was found that the second-order
irreversible
57
56
55
nitrobenzene-oxygen
trapping
rate
of
constanis
efficiency
the counterions
for
ionization
are in the order
and for (CH314N*
~l~~Y,OCH3~~ilaOCil3--LiOC~3_ Benzhydryl by lithium
results
These
chlorides radical rate
are conirasted
to similar Similar
in the reactions
mass spectrometer
and absolute
gas phase acidities
Such acidities
transfer
reactions
mechanism [102]_
of corresponding
mechanism through a geminate
mechanisms are suggested of diphenylmethyllithium
is of
is discussed.
rates
of a variety by pulsed
The relative
of several
since
to explain
the
with benzylic
of
anions
resonance
acids
[103]. of sol-
the measurement of oroton-
with related
spectroscopy
58 and 59 towards
why desired
electron relative
and the importance
Another paper describes
to determine
in a pulsed it discloses
carbon and nitrogen
acidities,
of delocalized
ion cyclotron
reactivities
in an effort
generated
interest
are compared to solution
energies
as determined studied
coupling
gas phase carbanions
hioh-pressure
transfer
to ethane derivatives
displacement
and chlorides.
A paper describing
vation
have been dimerized by a classical
via an electron
intermediate_
differences
fluorides
apparently
which occur pair
fluorides
and benzyl
naphthslene
alkyl
neutral
halides
ranoalkylations
species
[104]. have been
of species
like
14 58 afford
of mono- and dialkylated
mixtures
that such carbene
anions
of the more substituted
suffer
products
dialkylation
The authors
[1051. of
because
the greater
conclude
reactivity
anion.
58, R = H 59. R = CH3 The equilibrium lithium
anionic
polymerization
of n_-valeraldehyde
benzophenone has been investigated
of -5.3-0.3
kcal/mole
and -25.7r1.4
cal/mol-deg,
effected
by
Enthalpy and entropy
[106].
respectively,
values
have been dis-
closed. Equilibrium ters
solution
acidities
of a number of phosphinylacetic
in diglyme and in DMSOhave been disclosed
it has now been established are observed tions
that kinetic
not only with different
The kinetics
of the disproportionation
of the alkali
illustrates dianion
cation
salts
by fluorene solvents protonated
ion pair
is protonated tight
tTll]_
tetracenide
four-five
The kinetics
alkali
ca-
The study
radical
anions.
orders
of
species
faster
than the cor-
fluorenyllithium
the former system reacted
and solvent
has been
separated two-three
ion times
one_ of alkali
derivatives
of the cation,
to the tightness
with the potassium
of ethyl
the solvent,
of ion pairs
[112-J.
than with the lithium
of the solvents
acetoace-
and the alkyThus, more salt
and in
are deemed more important
than
constants_
Other kinetic
studies
and lithium and styrene
have been performed [113],
n=butyllithium
on the systems bromobenzene, and 4-methylmercaptoaceto-
and lithiumdiethylamide[115].
in the area of stereochemistry,
the Z/E equilibrium
is
and that the sodium
of magnitude stuay.
of ethereal
the lithium
ion pair.
carbanions
and sodium
in a variety
ion oair
an-
for certain
1,3-diphenylallyllithiun
revealed
RWA than DMF- The ionicities
phenone [114],
corresponding
of
In another
of 0- to C-alkylation
dielectric
radical
as a func-
[109].
free
than the latter
is realized
photolysis
favoring
agent and is ascribed
benzaldehyde,
flash
than the tight
has been found to be a function
0-alkylation their
of alkali
spectrophotometrically
ion pair.
under conditions
The ratio lating
Hith different
it was found that the loose
lithium
more rapidly tate
but also
ones may be responsible
than their
the protonation
about 100 times faster
responding pairs
of C-H acids
have been determined
using
than steric
have been determined
[llO]_
alkylated
other
being more stable for
dianion
and solvent
that factors
Rate constants
tight
effects
espaper.
[lOS]_
ions to the parent compound and its tion
differentiating
anions
acid
In an unrelated
[107].
compositions
of
15 several
E-alkenyl
been studied the Z/E ratio endo (cis)
organometallics
as a function increased
preference
60 (R = CH3. CH3CH2, i-C3H7. f-C4H9)
of cation,
in the order
R, and solvent
[116]_
Li
between R and the alkalimethyl
pendent on the electronic
capacity
or the size
carbon
of R.
have
It was found that Moreover,
the
seemed not very de-
Reasons are suggested
for
the above observations. RCH = CHCH2M 60 3-#ethyl-Z-pentenyllithium hydes , acetophenone,
mounts of branched factors
[117]_
p-electron
has been condensed
acetone, (61)
and linear
The ratio
withdrawing
alcohols
of 61/62
groups_
ing groups _ Only 61 and only The results
respectively.
with a variety
and hesafluoroacetone (62)
decreases
a-
electronic
with o-electron
VJith acetone
in terns
of
of benzaldehydes
is realized
62 are obtained
are interpreted
as a function
in reactions
The opposite
of benzalde-
to study the relative
with donat-
and hexafluoroacetone.
of hard-soft
acid-base
theorv. OH
OH
/+AR
-_-
-_.. >
i 62
61 The effect
of
has been studied higher cifically
alkali
metals
with methyl
gave nearly alized
ion pair [llS]. iodide
a SO-50 mixture
in terms of a cation
63
siructures
in THF by varying
on the methylation
the cation
Thus, while to afford of mesoside
the lithium
meso-
of nethyl
64
salt
(:- 99:),
and racenic-64.
approach
stereochemistry
systematically
from lithium 63 reacted
iodide
63
are ration-
to diastereomer
65
to the
stereosae-
the rubidium salt The results
of 63
65.
16
i4etalation
to afford
of
(+)-(S)-3-methyl-Z-pentanone
(S)-enolate
has been reacted give optically
67 with less
with alkylhalides. active
hy LI\IP&has been show
(66)
than 10% racemization acid
chlorides,
Reagent 67 and ketones
to
products _
0
Oti
67
66 In the continuation of addition
[119].
aldehydes,
reactions
of an earlier to carbonyls
study concerned
with the stereochemistry
in terms of orbital
factors,
the relative
amounts of 68 and 69 from 4-t-butylcyclohexanone with MCH2Y\-rere found to vary Thus, less 69 was obtained with LiCH2Y than with the metallic cation [120]. with BrZnCH2Ywhere Y = C02C2HS. CONR2, CIi. and CO2M.
69
68 Several afford
ester
the 1,2-adducts
terestingly, ing,
lithium
the thermodynamically condensation
have been*condensed
70 at -7g0 by a kinetically
when the reaction
a similar fordino
enolatrs
mixtures
controlled
are allowed 1,4-adducts
with a lithioacetonide
with 2-cyclohexenone
controlled
process
to
[121].
In-
to warm to 25” before quenchIn one case, 71 are obtained.
was found to.be
irreversible
af-
only a 1,2-adduct.
LiO
t;i
+
CH3$Cfl$H3 X
The intermediate lithium
-7 71
(X = CH3.0Ph.OCH3.SPh.SCH3)
70
dimethylcuprate
ium enola:e
organometallic
to enone 72 has been found to consist
73 and insoluble
troscopy
[122].
probably
intermediates
obtained
from the conjugate
(CH3Cu), precipitate
It is suggested in all
even when the organocopper
that
lithium
such conjugate
product
as evidenced
rather additions
remains in solution.
X C02CH3 addition
of
of soluble lithby 13C RMRspec-
than copper of lithium
enolates cuprates
are
li
OLi
0 ether
(CH3)2CuLi
73 Other sutudies (S)-lithiobenzyl acid
[123],
in this
the stereochemistry
dihydroanthracenes valent
[124],
phosphorus
nethoxide
to afford of
the silylation
and the inversion
atoms of two phosphinate
with the carbonation
of
(R)-:i-nethylsulphinylphenylacetic of 9-alkyl-lo-lithio-9,lo-
of configuration esters
at the chiral
by methyilithium
tri-
and sodium
[125].
Several 1976.
area have been concerned
methyl sulfoxide
papers describing
A continuation
has resulted
in the discovery
control
[126].
erythro
acid
For example, enolates
has also
of organolitiiums
of the ester
enolate
of solvent
that choice lithio-(E)-crotyl
75 in TtiF and to threo acid
Z- and E-type
reaction
rearrangements
of the study
appeared
Claisen
dictates
propanoate
in
rearrangement
stereochemical
(74)
rearranges
to
76 in THF-HHPA. It is suggested
This
are formed in THF and in THF-HHPA, respectively.
been employed in the construction
of the prostanoid
[127]. H
H
that
skeleton
-
CH3
” vCH3
.-
OH ti
of alkali
The isomerization all
for
cis
77
_‘._ _:
and potassium
cations,
been effected
by protons
anion 77 to the
a much higher
where the &Gf of the isomerization
lithium
of 77 to 78 has also
.;
cis,cis,cis.trans-[gjannulene
78 has been found to require
than topomerization kcal/mol
76
74
75
more stable
OHH
0
CH 3
respectively
activation
energv
ranged from 29.6-34.3 Isomerization [128]_
and by photochemical
78
and thermal
16
A fuT1 paper appeared describing
with cholesteryl ring
systems participate
found for result,
Several
ring
salts
the Stevens rearrangement ethyl,
tosvlate.
reactions
were
As a
which occur
sp3- carbon atom_
of methallyamines
have been subjected
to
to 82 and 83, respectively_ %th larger alonly 82 arisinq from 80 was ohserved.
81
80
i
R-R’
R’
83
82
86 [131].
results
and cyclohexyl,
R /J ’
Quaternary salts
Similar
and other bases [130]. When R and the reaction proceeded via a mirand n-butyl.
79
bases to afford
dialkylcuprates
by n-butyllithium
n-propyl,
i-propyl
lithium
[129]:
in these
at the nucleofugal (79)
ture of 80 and 81 which rearranged kyl groups like
reactions
are observed
of configuration
of
in which the double bond of the
of cyclopropylmethylcarbinyl
reorganizations
quaternary
R’ .were methyl,
tosylates
in substitution
the cycTopropane
skeletal
with retention
the interaction
and 5-norbornen-Z-y1
84 (X = Cl,I)
Stevens rearranged
The amines arose
were also product
treated
from a cormnon intermediate
a5
with a variety
85 and Sommelet rearranged
a6
87.
87
of strong product
19
Similar
have been observed
rearrangements
amines 33 and benzyne.
generated
[1323.
Among the products
induced
by excess
in the reactions
from o-fluorobromobenzene
observed
of silyletkyl-
and n-butyllithium
The cyclization
were 89-91.
to give
90 was
n-butyllithion. :*3
Certain sulfones step
like
h-arylbenzenesulfonamides 93 upon treatment
in such reactions
fonyl
like
92 have been found to rearranqe
with organolitkiuo
is metalation
91
90
89
88
of a ring
reagents
[133].
to
The first
hydrogen atom ortko
to the sul-
group.
93
92
The previously
reported
found to be reversible lithium
counter
[134].
rearrangement
stabilities
Na
I
I
Pk C-R 2
N-Ph I
to 94 by tke use of
of sodio-95
c0zc2*5 Ph2‘,
of 94 to 95 has now been
Thus, 95 may be converted
The relative
ion.
discussed.
1,2-anionic
,’ \
versus
lithio-94
are
C02C2H5
-Ph
Li
95
94
Ketazines their
have been converted
Jilithio
is determined
salts
as illustrated
to pyrroles
or tetrahydropyridazines
in Scheme I [135]_
Which nroduct
via is formed
by the nature of the R and Ar groups.
R mechanism has now been proposed for the conversion of 96 to 97 involving, lithioaziridine 98 which has been trapped among other proposed intermediates, with methanol-O-d
[136].
0
0
P
NH-c-C6Hll
I c-C& 96
1
Ph 97
I c-C6Hl 1 98
20
Scheme 1
Ar
I
Products from
the
99-101
tiittig
(R = 5-hexenyl
rearrangement
by n-butyl-
and methyllithium
group
via
arise
of
pathways
secondary recombination of alkyl to 99-101
which
contain
the
orcyclopentylmethyl) benzhydryl
[137].
intramolecu’lar
2.2-3.0 LDIpA THF
radical
Ghexenyl
have ether
in
been obtained THF effected
Those products containing the 5-hexenyl which
may involve
and ketyl.
cyclopentylmethyl
group
routes
other
The cyclizations are
said
to
occur
than leading with
5-
21 hexenyl
radicals
which escape
with appropriate
reaction
with geminate
partners
but later
react
ketyls. R
!
; &
Ph2C-OH
.cFL/
*6&.Ph P”.
_. -’
( Ph 99 Two papers discussed siloxybenzenes. lustrated
and other
pyridines.
by the conversion
some cases,
of
fail
[lSO].
a portion
the synthesis
rides
4.
of
substitutioh
in contrast,
il-
route
in
1 ithio-‘J-
of the first
in the reactions
have been concerned
with the con-
rearrangement cyclophane
of a dithiacyclophane
within
a cyclophane
as
[ICl],
and
of tributylstannyllithiun
with aromatic
fluo-
have been metalated
by n-butyllithium/T!-?EDA
c142].
METALATIOZS A.
At so3 Carbon Several
polymethylbenzenes
in hexane to afford tion
The process,
to (El-2,2-diphenyl-l-methylthiovinyl-
the us;? of the Vittig
and chlorides
in others.
rearrangements
of 5,5-diphenyl-4-thiacyclohexene
cyclopropane tine
route
[139,139]_
by an intramolecular
to undergo such rearrangenents-
Other papers discussing version
heterocyclics
102 to 103, occurs
but by an intermolecular
iriaiky1silylarylaaines
101 in lithio-O-trialkyl-
100 anioni c 0 to C rearrangements
[143].
clusively
di- , and trilfthio
mono-,
For example.
mesitylene
The energies
105.
and are included
derivatives
gave mostly
of these and related
104 while species
as evidenced p-xylene
by silyla-
yielded
ex-
have been calculated
in the paper. CHLi2
CtQLi
2Li+ LiH2C fiCH.$_i
@ CH3
104
105
106
33
Four methallybenzenes above reagent
to afford
and isobutene
corresponding That dilithio
by methyl bromide [144]_ :!HR spectroscopy.
The methylated
enes were obtained
in preference
discuss
at great
methane dianion Metalation lithium
the
species
at a benzylic formally
carbon
delocalized
was confirmed
from cross
from linear
of the aromaticity
by dimetalation
of
by the
which were methylated
were present arising
to those arising
question
obtained
metalated
derivatives
derivatives
of 1.2-dihydropyrazines
occurs
tem containing yields
length (106)
have been similarly
dilithio
conjugated
ones.
by di-
The authors
of the trimethylene-
isobutene.
107 (R = Ph or p-ClC6HS) with n-butylto give
bicyclic
Sn-electrons
108 rather
[14S]_
than 109, a sys-
Hydrolysis
of
108 then
110.
108
107 A combination
of metalation-metal
lithium-potassium ene(lll)
t-pentoxide
to dianion
112, a very stable
ple cycloheptatriene cloheptatrienyl
hydride
[146].
elimination
reactions
has been emp!oyed to convert species
Oeuteration
of
by n-hutvl-
l-methylcyclohept-?-
which does not behave as a sin-
112 affords
the known methylenecv-
anion 113.
111 !*letalation
of
112
squalene
113
by s-butyllithium/TMEOA
has been found to occur
only
on a methyl group [147]_ prenylamine
In another paper. metalation of a methyl qroup of 114 by n-butyllithium results in an interesting isorrerization and
elimination
to give
isoprene
[148].
Other related
examples are listed.
114 Polymetalation tion yield
of acetylenes
continued
of 1- and E-butyne and 3-methylbutyne CH3C3Li3 and (CH3)2C3Li2,
densed with a variety
respectively
of electrophiles
to be studied
in 1976.
with alkyllithiums [149].
to usually
Thus, reac-
has been shown to
Such species have been conafford polysubstituted acety-
23
lenes of
and allenes
like
are best
described
sequential
soft
scribes
of
[lSOj_
The results
and acetylide
A second paper in this
are ascribed
sites
allenynes
C3Li4 gives
mostly
to proparqylic
sites
and reactions
and diethyl
C-CCC-Si(CH
)
(f!J3)p
(CSIj3
120-122
lithi?;n
C2%\ .=C=c~C2ii5 /‘Si(Ck!3)3
Zhile
[152j.
r20 and 122 were netalated
to afford
The authors
suggest
by n-butyliithiun
which have been condensed
121 gave a mixture
respectively.
by n-buty’llithium
have been mecalated
reagents
120 Regioselective dimetalations (123)
124 after
122 with chloroirimethylsi-
,Si(CH313
(CH3)3Si ‘C=C=C / &J ) .. ‘2 4
(CH2.i4
CH2-C-C
/
124
123 Seven I-arylpropynes order
rea-
on 1,Scyclotetradecadiyne
quenching
i CH2CXCH2
and trilithiated
of
only at the methyl and
that both netarations occur .ztthe same car-
CH2CXCH2 ‘.\ / (c\H2)3 (CH2)3
Pseudo-first
to
with a variety
of .I- and -:‘-nonolithium
121 have been e ffected
bon atom.
di-,
of which gives
113
proparqylic
lane El53].
being
paper de-
117
33
Cyciopropylacetylenes
carbon,
sulfate
A third
(C,E,),C-XX--Si(C1!3)3
L
118
electrophiles
and chloro-
[llj].
AE
Si
i-ring
hard.
116
2 5’2,
discussed
sulfate
of CH3C5Li3, derivatization
(CH3:2C=C=C,r
115
yield
series
species
117 alonq with some 118
being
and some cumulenes and diacetylenes
i
containing
by diethyl
and chlorotrimethylsilane
!CH3)2;4:c-E
(C 2.1
of which depends upon the size
the above lithium
these organometallics
For example,
the preparation
mostly
ratio
the
as proparqylides.
derivatization
trinethylsilarie and 119.
115 and 116,
An IR study suggests
the electrophile.
containing
various
ring
substituents
on the methyl group as evidenced rate constants
for
have been mono-,
by silylation
the monometalations
[154j.
were calculated-
24
Several
methyl ketones
have been regiospecifically
methyl carbon atoms with aldehydes 126
rl55-j.
by bulky
The success
bases
like
127 in the presence
enolates
that o-methyl-hydroqens
in preference
to p-methyl-hydrogens,
fects.
An additional
-c-hydrogen may also
of an acetylene
lithium
in hexane to give
ionized
via eliminaiion
probably be abstracted
of lithium
trilithio
too weakly
and o-hydroqens leading
ef-
to the foma-
salts
the conversion
131 by LDIPA in THF [158].
using alkali
metal
amides
failed
of triketones
Previous because
attempts these
like
130
to pre-
reagents
are
basic.
A similar
lithium
cyclohexyisopropylamide,
was found necessary
to
of 132 [159].
Lithium enolates fragment as indicated Glycidic
methoxymethyl
132
131
base,
ionization
134 [160].
are
of chelation
129
131)
effect
128
,CH2Li
paper has appeared describing
pare such trianions
like
oxide.
128 to their
SiZ
have been
species
because
,CH3
A full
[156]. .x \ Si
127
by n-butyllithium/TKDA It was established
and 129 [157].
Similar
co-reagent.
from esters
0
ring mono- and trimethylacetophenone
metalated
of 125 to
the metalations
126
125
tion
the aldehyde
OH
Several
td effecting
E-hydroxyesters
n
further
of
on their
by the conversion
of the method is ascribed
have been employed to prepare
bases
as illustrated
condensed
esters.
from methoxyirethyl
esters
at 25” and recombine esters
may be prepared
like
to afford similarly
133, though stable
at -79”.
hydracrylic
like
esters
by metalation
of s-bromo-
Lit
0 /CH20r-i II -- R2C=C=Of H-C-H + LiOCH3 - R2C
3: R2C_E&CH2&-CH3
\
+LiOCH3
133 Lithio-t-butyl talation
of
dehydes
to give
pared simi?arly, [162].
silylester
acceotors.
reacts
(135)
esters
[161]_
Lithio-t-Duty7
with aldehydes
have been (1361,
-:,:-unsaturated
prees-
-_si __-’
ester
enolates
of undergoir;g are
generated
like
thio
by LDIPA at
as Part of
I! R’CHpt 139
to be metalated
organolithiums
to afford
have been
0
138
the resulting
ester
(1381
139 [163].
[164].
As fLi continue
like
with formaldehyde
0
esters
and ketones
esters
the parent
been condensed
137 thio
[166].
of
thiol
of u-methylerie-y-thiobutyrolacione
i CH2=CSR
For example,
to afford
by metalation
OLi
Certain
137 and ,-thiolbutyrolactone
al kylation
136 has also
Lichiolactone
the preparation
alpha
io sulfur
by LDIPA.
140 and 141 have been condensed with
a,?-unsaturated
esters
[165]
and chiral
thi-
respectively.
S(O)
S I!
Li
LiCH2-SX-OR
RO:, , CHC02C2.H5 S
141
140 A variety of
al-
ii
thio
The enolates
tions
of
tl
Lithium
metalated
by me-
a variety
esters
to yield
Li
found capable
iranes
The latter
and ketones
!
aldehydes
with
trimethylsilylacetate
(ESi)2
-73”.
-
has been obtained
by LDIPA and condensed
vinyl
a-silylated
shown to be Michael ters
134
bis(trimethylsilyl)acetate
the parent
co2cc;3
of phosphate
by n-butyllithium 143 with aldehydes
esters to give yields
0
I! _
R2C=;-CH20P(OC2H5)2 R
142
and phosphoramides intermediates
like
like
142 have been di-
143 [167]_
lactones.
.+ 0
‘I’
R2C-7Tq
II (OC2H5) 2
R 0-Lf+ 143
Condensa-
Interaction of N,IJ-dimethylbenzamidewith LiTMP to afford 144 proceeds via The latter organolithium reagent may arise the dipole stabilized 145 [168]. from metalation
of the methyl group syn to the carbonyl a related carbanions are described,
oxygen. reaction
examples of similar ethylbenzamide
results
tional
In a different
group_
mide by s-butyllithium more stable
only
in ring metalation ortho to the carboxanide funcof !1,M-dimethylthiopivalapaper, the metalation
to afford
146 is discussed
than 145 is evidenced
with alkyl
halides,
nucleophilic
aldehydes,
by its
ketones,
aninoalkylation_
[169].
That 146 is apparently
sufficient-life-tine to be condensed Such condensations represent and OHF.
_
146
145 Hippuric
has been converted to its
acid
and then al kylated
to give
similarly
and condensed !_i
prepared 0
148 [1703.
trilithio
Dilithio
salt
salts
with alkyl halides !
YH.I_.
147
Li
of 151 with LOLPA has yielded
yields.
nuder
of alkylating
Similar
as part of the synthesis
i
metalation
/R
;
\-
like
Subsequent
gave d,S-unsaturated
of acrolein
of species
150
152 [172].
agents
OSiZ
OSiE R
Oh
0
of 152 with a large ployed
,/ 0
148
149
in excellent
F
Li
ii lletalation
147 by LDIPA/TMEDA
149 and 150 have been [170,171].
Ph/9
0
Though other on II,N-di-
cyanohydrin
153 11731.
reaction ketones
has been em-
m-Tolunitrile ford
has been metalated
154 [174]_
Condensations
In a different reacted ducts
study,
with various arising
for
the first
with ketones
the three
isomeric
time using LDIPA to af-
and alkyl
halides
are described.
bis(cyanomethyl)benzenes
amounts of methyl1 ithiu ii: and methyl iodide
from multinethylation CR
[175].
155 have been to give
pro-
CIi,CN L
0 a L:
CH2CN
\.
154 papers disclosed
Several with bases
additional
such as LDIFA, lithium/diethylamine
ethylamide.
Such netalated
amines like
kyl halides
[176],
:l-bromoacetals
haloalkenes
[179].
epoxides
imine has also
been cetalated
ot- ii-alkylated
as a function
!177],
dihaloalkanes
and chlorotrinethylsilane
the cation
156
imines
156 and 137 have been alkylated
by netbyllithium of
of
in benzene/RMPA, and lithium
and ketals
[180].
155 of the metalation
exa::ples
to give
[178],
[lSl].
di-
by aldi-
A bis-
158 which has been C-
and solvent
[182].
N
157
Ph 158
In the area of oximes,
the position
Governed by the configuration and condensations
with aldehydes
Thus 159 and 160 afford cyclic
ketones
iodide
occurred
lithio
oximes have also
azoles
[187]
Several after
like
oxines
and their
the axially
[183]
also
work up. hydroxylamines
has been shown to be
and ketones
and by deuteration
[184]_
product
al kylation
[185,186]_
chlorides
to qive
P-isoxazolines
of organolithiums
4-acylisox[ls8]. to afford.
_ Lit R
HO,
160
161
162
by methy
Such di-
163 [189]. Li+
159
alkylation
In the case of oximes from
to yield
underwent addition like
by subsequent
O-methyl ethers,
substituted
been condensed with aroyl
and with aldehydes
lithiated
and ketones
161 and 162. respectively.
cyclohexanone
to give
of -;-netalation
of the oxime as evidenced
163
28
A large
number of N-N-dimethylhydrazones
tones have been regiospecifically
[190,191,192]
ety of electrophiles aldehydes
[191],
to afford
polyfunctional
The use of chiral
chiral
ketones
enolizable.aldehydes
by LDIPA
to give
a;ld ke-
derivatives
[190,193],
v-hydroxycarbonyl.
compounds [192],
165 in alkylation
1,4-
164
with a vari-
aif!-unsaturated
and l,S-dicarbonyl
and a-thiomethyl
reactions
like
species
164 and 165 have been reacted
alkylated
6-hydroxycarbonyl.
compounds, other c1943.
metalated
Reagents
and 165 [193].
of
gave,
after
compounds hydrolysis,
[193].
(CH3)$\ N Li * ,C
‘c
/
iin 165
164 Several
other
phenylhydrazones,
zones have similarly certain All
hydrazones
of these
sis,
tions
168 affords
alkyl
active
halides
ketones
enamines from certain
n-butyllithium
species
to give
trilithio
[199].
chiral
166 [195.196]
reagents
[198]_
sulfate
In a different
indanones
The results
lithioenamine
and dimethyl
like
while
167 [I??].
169 which has been to give,
paper,
and a cyclopentenone
obtained
from subsequent
after
hydroly-
metalation
of pyr-
were effected methylation
by
reac-
are presented.
169
168 Allyloxy lyl
and N-p-tosylhydra-
like
have been condensed with electrophiles. Li
of chiral
by several
optically
rolidine
to dilithio
have been metalated
reagents
Metalation alkyiated
N-benzoylhydrazones.
been converted
ethers
with aldehydes Internal or chloro
carbanions
like
by s-butyllithium and cyclic
cyclization
172, condensations
ketones
reactions
substituents
170 continued [200,201,202].
[201].
to be prepared Condensation
gave mostly a-type
by metalation of
products
of 170 have been observed
of al-
170 (R = Si(CH3)3) like
171 [200]_
when R contains
epoxy
In the case of the related pentadienyl lithium with a variety of electrophiles usually afforded mostly
29
y-substituted
products
like
173 [ZOZ]. Li+ .++
+,
Li
OSiR3
OR
Metalation
of propargylic
banion which reacts Hydrolysis
of
& P
174
Certain
acetal
with alkylating
the resulting
as if
illustrated
z,fi-unsaturated
Phi-‘-\e
derivatives
of D-arabinose of
a car-
175 [203]. esters.
175 and D-fruciose
to cause the elimination
by the conversion
gives
it were exclusively
yields
q/-
with n-butyllithium
The process,
174 by n-butyllithium/TYEO4 agents
ketone acetals
0-isopropylidene
‘been reacted
173
172
171
170
of acetone
176 to 177, apparently
have [204]. involves
ring metalaiion.
?H
HOCH2$H-CH=CH-C(C,H9)2 OH 177 Lithiation Phinyl,
of
178 and phenylated
PhenYlsulfonyl,
derivatives
1.2-epoxyalkyllithium
rea9ents
densed with
of electrophiles-
a variety
where R is a silyl,
and cyano stereospecifically
ethoxycarbonyl,
Such reagents
179 ~205.206].
phosaffords
have been con-
178 Choice of lithium gives
of solvent diethylamide
has been found to be very important in the interaction For example, 180 epoxides [207]. with -.,,S-unsaturated
181 and 182 in ether
182
181
180 Q-Ketosulfone
and HYPA, respectively.
183 has been converted
by LDIPA, then alkylated
to its
by 1,3_dibromopropane
corresponding
[208].
diiithio
salt
Subsequent cyclizations
30
via either
C- or O-alkylation
similarly
been prepared
then condensed with cyclopentanone
acids,
Dilithio
are described.
from the corresponding
salts
sulfinyl-
to afford
-f-lactones
Other sulfur-containing
organolithitun
reagents
prepared
the parent compounds have been 186 used in the synthesis 187 used to prepare monothioglycols
[Zll],
PhS or Ph2P0 used in the synthesis
[209]_
185
184
183
Z=
184 and 185 have
and sulfonylpropionic
and acyl
of certain
by metalation
of pillarose
anion equivalent
ketones
12121.
FI &H2Li
CY ‘\
Lid A full has appeared
L-2131.
SCH., J
187 the preparation
186 paper describing
189. prepared
Species
butyllithium. was condensed useful reactions_
with a variety
by metalation
Hydroxytin taining
reagent
190 with n-
in synthetically 0
been converted with alkyl
193 [214].
of a-vinylbenzyl
189
190
by reactions
compounds to afford
the conversion
anion
Ph3P a
191 has possibly
as evidenced
of ylide
+
189
butyllithium
Li
of ylide
of electrophiles
Li
188 u&-e
188
and reactions
0 Ph3i&
of
[ZlO],
A full
alcohol
to dianion
halides
192 by n-
and carbonyl-con-
paper appeared which discussed
to a dilithio
salt
[215].
OH
H--c H
Sn(n-C4Hg)3
H
191 A variety afford
species
trophiles
i
H_ 192
of nitroalkanes like
to give
194 [216]. 195.
193
have been doubly metalated Such reagents
by n-butyllithium
were condensed
to
at carbon with elec-
31
R-CH-X02 ; 195
194
Finally,
organolithiun
reagent
196, prepared
equivalent
derivatives
number of
to give
Organolithiuns
similarly
obtained
j
:,, R
-.
aryl)
\
Li-
Compounds like
R
by t-butyllithium
[221].
202 was demonstrated
netalation
In another
of ene-sulfides
ated faster
study
versus
than the latter
predominated
290
That such reactions
to sulfur
203.
0
which contain
talation
to afford
ones [222].
Vinyl
occurred
by condensations
involvinq
ene-ethers,
both alkyl the site
a comparison
me-
regiospecificalwith electroof the rates
of
rather
than ally1
metalation
with such ene-sulfides. E
203
202
201 In contrast hydrazones like
1
RSC=CHOC2HS
RS;=CHOC2HS
RSCfi=CH0C2HS
to References 190-194. interaction of branched :1&dimethyl204 with lithium in diethylanine/benzene/HMPA affords nitriles
presumably via vinyllithium densations
(or aryl)
of vinylic
the former compounds were metal-
Li
eliminations
like were
Li -i
,R
to determine
ly alpha philes
and 2110 [220]
199
have been studied
to give
afforded
species
?!\_/4
3.’
201 (R = Ph, n-CSHl,)
groups
to yield
forma-
and ketones_
I’ ‘,
198
and alkoxy
Com-
of a large
with LDIPA at -100”
of electrophiles
with aldehydes
atom of
Thus, treatment
0
2’
197
thio
the sp2-hydrogen
carbanions.
5
I! \l/
E-
[217].
carbanion.
199 (R = C1f20CH3and CR3) [219]
and reacted
5
Li-'
of
(R and R’ = alkyl,
197 which was condensed with a variety 193 CZlR].
to a formyl
rretalation
unmasked acyl
formar;ides
of the parent
to aldehydes
XITROGE:i
Three papers described nide
by netalation
ihen oxidized
compound by LDIPA, has been alkylated pound 196 is thus synthetically E_ AT so2 C4RBO;lAXD AT
196
reagent
with a-hydrogen5 with alkyl
halides,
205 [223].
underwent in situ aldehydes.
The product
metalation
ketones.
nitriles
from such
as evidenced
and epoxides
[224].
by con-
205
204 Diazo compound 206 has been metalated 207 [225]_ tones
This lithiated
to afford
species
208 (65-8OZ)
by n-butyllithium
has been reacted
at -100”
to give
with benzaldehyde
and ke-
which has then been converted
to epoxides
and al-
dehydes _
OH
298
207
206 Theunderlinedallenic ated by n-butyllithium
hydrogen atoms in compounds 209-212 and subsequently
replaced
by alkyl
groups
H
Y qzC’C’$JHOH
have
been metaf-
[226,227].
,CH20H
‘C=C=C \
H’ =
ti
CH3 210
209
? tH3 (RO)*P-N-C;&* 211 Terminal acetylenes with n-butyllithiom ides
to afford
electrophiles lithium
214
with propargylic
to give [228].
hydrogen atoms have been dimetalated
213 which reacts Such alkylations
at the terminal
carbanion
systems have been condensed
regiospecifically are
to yield
with cuprous
to give octamethylcyclododeca-1.3.7.9-tetrayne [230],
respectively. Li
RA
*
213 Turning
stituents
[231].
by reactions
215.
Other acetylenic
chloride
[229]
and acetic
acid-D-d
RA,
‘E
’ Li compounds,
by n-butyllithium
The following
to
214 a large ascertain
order
other
carbon-
R’
RA, . Li
hal-
uith
and monodeuterioacetylene
R’
to aromatic
were metalated
with alkyl
followed
number of a ranking
215 p-substituted of
has been established:
anisoles
ortho-directing
-S02N(CH3)2.
-S02NHCH3, -CONHCH3,-CH2N(CH3)2 =- -0CH3 > -CH2CH2N(CH3)2. -NME2. -CF3. F.
sub-
33 Similar
results
The effect
were established
of TMEDAin such directed
.A regiospecific
route
o-metalating
and hydrolyzing benzamides
several
was studied.
aryl
ketones
the carbonyl
with n-butyllithium, been o-metalated
has been effected
by
group of :i,:i-dimethylbenza-
condensing
The mathod is illustrated
[232].
have also
o- and m-substituted-anisoles.
metalations
to o-substituted
reagent, = across
adding organolithium mides.
for
with various by 216,
and condensed
electrophiles,
217, and 218.
with electrophiles
Thioto afford
219 [233]. LiO
5
0
R
LiO
R :I(CH3)2
Metalation
of several
has been shown to give ganolithiun
reagent
parent methylenedioxy
220 [234].
223,
of these
lithiated
The site
with dimethylaminomethyl. of the ring
stituted
thiophenes
Z,!i-disubstituted mediates
225 [237].
metalations
of thiophenes
and carboxamides [236]_
substituted
was shown to be a Thus, 2- and 3-sub-
in the 5- and 2-positions,
systems were metalated
[235].
with electrophiles.
of the substituents
were lithiated
were condensed
Other directed
directed
Or-
exchange of the correspond-
to 222 at ambient temperature
were condensed
methoxymethyl.
position
compounds by n-butyllithium
and 222 L-2351, respectively_
from metal halogen
isonerized
species
of regiospecific
function
221 [234],
prepared
ing bromo compound at -78”. All
219
218
217
216
respectively;
only at the 3-position_
Such inter-
with electrophiles-
metalations
methoxymethylferrocene ,N-Ph Ph2P_--
224
have been effected [238],
on imides
and ferrocene
225
like
226 to give
224 to give 227 [239].
34
227
In other work dealing duced by reaction of
with metaiation
I-methyl-5-methoxyindote
tive
giving
1inked polystyrene
organolithium
has been ring
and chromium species
followed
[241].
Also.
cross-
with n-butyl f i thium-WED& [2-‘2-2541
228 has been converted
with t-butyltithium
and 1ithiation
has been found to be nonse!ec-
intermediates
t i ttiated
benzyne has been oro-
with LiTXP [240]
with n-butyllithium
three different
metafation
of aromatics,
of phenyl benzenesulfonate
to 229 (G = Si:,
by condensations
CO2Li, others)
by
with electroohiles
[245]. (Ph)Cr(C6F5G)
(Ph)Cr(C$5H)
229
228 Metalation give
231 to afford oxide, [24S].
of arylsulfonylhydrazones
vinyllithium
reagents
like
232 have been realized
aldehydes,
ketones,
230 by organolithium to be studied.
with dimethylformamide
and alkyl
X-!iHAr
R
like
231 continues hatides
[247],
[246],
)I
to give
like
233 have been treated
234, apparently
via ring-opened
Other examples are cited.
233
232
231
a-Epoxytosythydrazones phenylcopper
YE
Ri
R’ 230
carbon di-
PA
ji R>
to of
and chlorotrimethytsilane
R\;/Li
/
reagents
Condensations
234
with n-buty3lithium intermediate
235 [249].
and
Other re?+ted chemistry olefin
tosylhydrazone
of this
formation
functional [250],
methylbicyclo[4_1_l]oc afford
chemistry
the use of
this
ta-2,4-diene
diethynylcarbene
235 [252]
volving
the conversion :
for
nitrogen-containing Sy metalation.
ketones
aive
carbodiinides.
5.
LITljIUW
Lithium dichloroalkoxides
245 [260].
XD
while
to possiblv control
[25”],
239 [256]
dianion
242.
to give
Carbenoids
studr
(CH)12
hydrocarbon
R-X
242
at
170-209
nonto
O?.GR~~OLITHIiiYS
Subsequent
and the
treatment
a convenient
243 and 244 have also
Lithium dibromomethide
have also
donor and reduces
242 (X = Br) [259]
RUX’ x
and 249 [257],
have been added to ketones
241 [253]_
like
to afford
of an unusual
241
of mi-
and in a
1&C! decomposes
HALCGE!4-SUESTiTiJTED
and dibromomethide
and aldehydes
X
of
of 7,7-di-
238
species,
OTHE3
silylated
respectively_
the synthesis
bridge-bending
(X = Cl) or LDIPA (X = Br) provides like
with ketones
pyrolyses
Reagent 239 is a hydride
to alkoxides
CAP.fiEFOIDS
dihaloalkenes
[251],
237
iwo other
n-butyllithium
in the preparation
of 237 to 233 [255].
236
resulting
reaction
with the stereo-
to the regiospecificity
and to study stereoelectronic
12531 and as part of a test
been prepared
relation
fro::; *:-pinene
gration
enolizable
has been concerned
group and its
route
with to l,i-
been condensed
and vinyl
sulfides
has been employed ES part of [261]. CHO 25\::
/
C,H5D
\8rBr 243
Li
in-
36
c2*50,: SPh
/p X Cl
C2%0
A variety noids
\Li
of cyclopropanol
derivatives
Thus, treatment
[262-2641.
amides [26_3]. and 2-chloroethyl with large
[264]
numbers of alkenes
246 have been prepared
of 247 where R = alkyls
and acetylenes
to afford
246.
In the area of cyclopropyl 251 [265].
In a related
The preparation
study,
exchange [266].
Other examples of this
alcohols
addition
or diethoxymethyl,
then alkylated
of copper
249 (R = Irethyl,
via nucleophilic
Br
249 (R = vinyl
carbenoids,
to 250 by t-butyllithium,
by methyllithium cyclopropy?
248
247
R’ = H) has been converted cussed_
and
Li ROCCl2
246
to give
via carbe-
esters
with LiTMP gave 248 which were condensed-
RO u
lyzed
[262],
reagents
or hydro-
from 251 is dis-
R’ = COCH3) was converted
to the carbonyl
stereospecific
to 252
and halogen-metal
synthesis
of o-bromo-
are cited. Li
8r
R”
8r
Br
Br
LR: &y .&R &c*3 I< .R*
251
250
249
Carbenoids
containing
pared from 8,8-dibromo-
c2711. others
were thermolized
reagent
annelated
tyllithium
[272]-
[269] to six-,
OH
been pre-
or converted
Cyclization
have been realized
[267,
2nd nonenes [270].
seven-,
were condensed
and gemi-
and eight-membered
with
electrophiles
rings
while
to allenes.
253 has been generated
and a dichlorodisilane
cyclizations
have similarly
and 8,8-dichloro-3.5-dioxabicyclo[5_l_O]octane
Some of the above species
Organolithium
252
endo-lithium-exo-halogen
266].9.9-dibromo-cis-bicyclo[6_l_O]nonanes nal dibromocyclopropanes
\
followed
from the corresponding
by metal-halogen
of 253 led to 1.2-disilacyclopropane on bis(sily1)
bromolithium
exchange with n-bu254,
Other
system 255 with dimethyldihalo
derivatives of silicon, germanium, and tin to afford 256 [273].
3i
si\SiLC’ \
‘Li
254
253
257
256
258
(M = Si.Ge.Sn) Finally, to give verted
lithium
dichloromethanebot-onic to 258 by mercuric
to be useful
acid
has been condensed [274],
and vinyl
bromide [275]_
in transferi-ing
with trimethylborate
system 257 has been con-
Mercury reagent
isopropylidene
carbene
253 has been shown
to olefins.
ADDITIO:: AND SUBSTITUTIONREACTIONS
6.
A simpler dardization
method :han double
of alkyllithium
through a syringe acetic is
dichloromethide
acid
solutions
of butyl-
in THF until
titration
has been suggested
[276]_
tire yellow
procedure
ihe
or methyllithium
for
the stan-
involves
addition
to a weighed amount of diphenyl-
end point
due to dili+hiodiphenylacetate
reached. In the area of aliphatic
lithium
initiator
two equivalents
soluble
and aromatic
of n-butyllithium
The initiator
organolithiums,
to one equivalent
alcohols
alcohols
to give
allenic
lithium
to 261 and subsequent
of styrene
259 have been found to react
269 [27G].
Similar
hydrolyses
additions
to ally1
di-
by adding
of m-divinylbenzene
has been employed in the polymerization
Alkoxypropargylic
an efficient
in benzene or heptane has been achieved
with n-butyllithium
of butyl-
alcohols
[277].
and isoprene. and benzyl-
are discussed.
CH30 R+
=
R’
OH 261
260
259
Both ciscloalkenones
Fh----
TOH
and trans-lithiocyclopropanes
262
such as 263 to give vinylcyclopropanes
Functional ized
cycloheptanes
are thenobtained
have been added to alkoxycvsuch as 264 L279]-
by heating
264.
3s
OR
Tandem phenylation further
investigated
ketones trated
264
263
262
by phenyllithium-reduction
as a method of converting
to S,v-unsaturated by the sequence
aromatic
by lithium/amnonia %,2-unsaturated
hydrocarbons
has been
aldehydes
The process
[ZSO].
and
is illus-
265 - 266 - 267.
266 Phenyllithium to afford
and related
ketones
like
reagents
268 and esters
ed to z,.,“-butenolides
to give allylic
tain
at sulfur
sulfonate
boxylic
acids
esters to afford
sulfones
and carbinois
the nitrile
triple
via the intermediacy
[283],
[284],
Ar
/i
Ar’
and added to an aminoketone [285]_
by addition
In contrast
and methyllithium
Such reactions
In a different paper, ketones and non-enolizable nitriles [287].
R-k-
R-LNLi h
N\
lb- /
r
N‘Li
to earlier tetraene
results,
condensation
and diazomethane 275 [288].
proceed were syn-
&-’
273
272
_
with carbon dioxide
274 and non-cyclic
of butyl-
[286].
NH 271
with cer-
combined with car-
of 272 and 273.
NH
been add-
reacted
270
bond of arylnitriles
from pyridyllithiums
R-\t lithium
They have also 270 [282],
269
Enamidines 271 have been obtained
thesized
like
ofdibenz[b.f,l]azapentalenes
268
across
269 [281].
alcohols
to yield
ketones
as part of the synthesis
have been added to perfluoroanhydrides like
of cyclooctatetraenedi-
has been shown to give
tricyclic
39
275
274 Interaction been reported [289]_
of pyridine to qive
In contrast,
pyridine
reaction
gave mostly
:*ith those
obtained
278.
with metal-free
P-n-butylpyridine
n-butyllithiun
(276)
between n-butyl
277 and less
chloride
than 1% of 276.
and lithium
The results
Derivative
with magnesium species. l.fi-
in pentane has
but no 4-n-butylpyridine
metal in
are compared
277 might arise
from
. -.
_ ‘,
A
$+..A,
,i
W
Q
V
(277)
t ‘I
Li
276 Cyclic thioethers attack [290].
at sulfur
like
by t-butyllithium
The driving
force
for
to afford
such reactions Attack
benzhydr:;l ic carbanions
1i ke 281_
been realized
282 and its
dioxide
on thiete
derivative,
phinodithioate
esters
respectively like
278 ones have been found to undergo
277 279 and related
is ascribed
at sulfur
l,l-dioxide
[291],
ring opened products
by organolithiums
tc give
283 and its
and at the alkylthio
284 to yield
phosphine
sulfides
sulfur [292].
fi
,
..
\
I Ph279
Ph 280
281
Ph2P-S-R 5 282
like
280
to the stability
284
of
has also related of phos-
40 Epoiyethylsilanes tetraphenylsilane was determined
like
diisobutylaluminum
g-alkoxysilane acid
and anti-elimination
_.
J\
288 and 289,
respectively
12943.
arose
(RI” Li)
in THF or ether while
respectively_
is a function
of solvent
289 and ketals
[2g5]_
Thus, 291 OSiI
0
RARm*
R”
R’ ”
290
A variety
hemithioacetals
292 is formed in HMPAor TMEDA.
OSiz
SR
acetic
from syn-
L
288 of 0-trimethylsilyl
of reaction
(290) with organolithiums is obtained
jugated
or glacial
The olefins
R
287 The course
R+
an intermediate
t-butoxide
R)& Si;
using
:Ph
286 287 afforded
to 9-ketosilane
of hydroxy and trimethylsilyl,
+
and trans-286
0
which upon treatmen t with potassium
gave olefins
it
alpha to silicon
on both cis-
amines.
\
285 of methyllithium
Addition
to give
of 285,
are compared with those obtained Ph3Si
?
analogues
the carbon
chemistry
The results
and various
Ph3Si J
attacked
Similar
manner.
trans.-stilbene.
with phenyllithium
Using deuterated
[293].
that the phenyllithium
in a npn-stereospecific gave mostly
285 have been treated
and styrene
of allyl-
and saturated
291 lithium
292
reagents
have been added to con-
enynes 293 where R’ = alkyl [296] and amino or hydroxyl groups [297]. products obtained such as 294 are in contrast to 3.4- and mix-
The 1,2-addition tures
of 1,2-
and 1,4-addition
and magnesfum reagents,
products
realized
with corresponding
respectively_ R
organozinc
R
R”
_--
*i*
Condensation a+-dihaloalkanes
293
of dilithiobutadiene
and other
have been found to give
cyclic
di-
294
and triene
products
tion
at the most negatively
charged carbon atom followed
tion
to afford
ring
the smallest
possible
[2g8].
from 296 and 1,3-dibromopropane.
In other
been employed in the synthesis
of monoterpenes
ium has been added to benzyne addition products [300].
by secondary
For example,
papers,
dianions
from initial
alkyla-
295 is obtained
pentadienyllithium
12991,
with alkyla-
297 has
and cyclopentadienyllith-
to give phenylcyclopentadiene
rather
than cyclo-
=
0
__ - -. -._ 2LiC (4
295
A variety Among those
of annulenes
continue
to be synthesized
formed were 1,8-bisdehydro[14]annolenes [302-3051,
addition
with lithium
298 [308].
In contrast,
specific;
for example,
erythro
ratio
_-
giving
similar
a lrl
additions
the latter
reagent
have also
afforded
with a threo-
pyrimidine
derivatives
like
of certain
enolates
vinylogous
derived
the conversion
300 with chlorobenzamides
302 [309],
prostaglandins
in HMPA/benzene/ether [314].
like
trihalides
have also
been
[311,312].
303 by carbonyts
and other
electron
304 have been synthesized Such reactions
[313].
Methyl ethyl kinetic
like
and with Group ‘J
Such organolithiums
from 305 and ketones to their
) 32
ii
stabilized aldols
of 306 to 304.
been converted
6-hydroxyketones
y’jN(Cii
302
Turning to organolithiums groups,
0
been condensed
301
have also
alcohols
the cis-alcohol
Li
303 (M = P, As, and Sb) [310].
employed in the synthesis
tute
of the cis-trans
299
Lithium acetylides
kinetic
and
of 299 and 300 were more stereo-
ijOLi
-Y
298
withdrawing
[306],
of Sri_
Ph
to yield
acetylides.
was found to be non-stereospe-
mixture
0
301 to give
lithium
6,8,15,17-tetrakis-
[307].
to 2-phenylcyclohexanone
acetylide
using
[307],
a 6,17,23-trisdehydro[ZZ]biannulene
a 2.4.13.15-tetrakisdehydro[ZZ]annulene Carbonyl
Lif
207
295
dehydro[18]annulenes
cific
(&AJ-
enotates
and methyl propyl by lithium
and then condensed with aldehydes
using constiketones
diethylamide
and ketones
to give
0 i’
OH R6
A/+‘.
CH3- =
R”
R
The enolates annelating enolate
of several
reagent
to yield
310 via C-alkylation gave only 0-acyl
Sulfonium ylides butyllithium variety acids
been
[320],
The chemistry
of aldehydes. by certain
have also [319],
halides
of 309 with acyl
to yield
ketones,
esters,
to 312 by
313 [317].
nA
and carboxylic chlorides
and sulfenyl
sulfur,
disulfides,
313
and used in the total of dilithio
than y-products
( 2 fb - \..
and angelic
= 2Li+
0
1
illustrated In contrast,
acid acids
[322].
halides
anhydride
catalyzed
to give
of sativenediols
of a.&unsaturated
317.
314
by nethylene
synthesis
only y-products
and 3-methylcrotonic
c/”
salts of salts
317 [322,323].
gives
tiglic,
been alkylated
condensed with citraconic
Thus, alkylation
in such reactions
_&
and acylated
312
be studied.
R
with alkyl
reaction
314 [318].
butenolides
c-
has been treated
In contrast,
[316].
enolates
Ketone enolates
butynoic
(309)
with bi-
The lithium
311 (R = CH3. OC2D5) have been converted
thiolated
by cuprous chloride
senecioic,
have been condensed
compounds 308 [315].
derivatives0
311
H
tricycle
or LDIPA. then alkylated
of lithium have
to afford
(316)
cyclohex-2-enones
307 to afford
of cycloocta-2,4,6-trienone
chlorides
306
305
304
acids
continues
by 315 afford
studied
and 3-methyl-2-hexenoic,
[323]. R
k R’7 316
cuprates were 2-
crotonic.
R R>,/.
C02CH3
C02CH3
315
to
more cr-
the use of lithium
Among the acids
two
[321].
317
43
Trilithioitaconic
acid
to afford
u-nethylenelactones
similarly
been reacted
6-n-hexadecalactone
(318)
has been condensed with aldehydes
like
319 [324].
with certain
chiral
Dilithiopropiolic
epoxides
to give
and ketones
acid optically
(320)
has
active
[3X].
Li C02Li
Li02C
Li
ADLi
-EE
D. 318 Related 3273,
319
salts
coupled
of acids
have been oxygenated
with formaldehyde
Monoalkali
[329]. esters
320
carboxylate
[3X3].
with molecular
and condensed
anions
oxygen [326,
with carbon disulfide
have been directly
alkylated
A full of esters
paper appeared describing and ketones
cycloheptancne
(321)
[331].
sulfenylations
The process
and dehydrosulfenylations
is illustrated
by the conversion 0
SPh sodium meta-
LDIPA PhSSQh
periodat?
)
322
321 Lithium enolates bromomalonate
esters
by displacement
bine by conjugate
323 Benzylidene yield
of
to enone 322. 0
occur
to yield
[330].
of alkylidene like
succinates
324 to give
products
(323) like
of 323 on bromine to afford
have been condensed with 325 [332].
malonate
The reactions
anions which recom-
addition-elimination.
325
324 derivatives
of glycine
326 which can be alkylated
to give
esters
327 [333].
to 328 thus finishes
the overall
Potassium
may be employed instead
t-butoxide
have been lithiated
conversion
by LDIPA to
Simple hydrolysis
of “glycine” of LDIPA.
ph_--.z
Qfy-F.=
R 326
327
of 327
to higher a-amino acids.
328
f-l
Several cinimides
a-ltthioesters
like
and nitriles
329 to yield
papers, ethyl lithiofarnesoate oxygen and a-thiomethylation lithiodiazoacetate
products
0
C02CH3 I
o-~~ 1 ‘I’”
330 [334].
has been found to undergo a-hydroxy?ation
CH2G 0
[335],
with
and ethyl
332 [336].
c& d BF4-
N2CC02C2H5
330
331
332
derived
from phosphorus
esters
and amides have been employed
Reagent 333 has been condensed with 310 (R = H) as part of the syn-
as follows.
of a 1,5-methano[lO]annulene
system [33?]
and reagent
334 has been added
to ketones taining
suc-
In other
C0*CH3 329 Organolithiums
like
with methyl methanethiosulfonate
has been added to 331 to afford
&zA
thesis
have been added to N-protected
polyfunctional
as -part of a new spiroannelation leading to quaternary Oiethyl-l-‘alkyl-2-oxoalkanephosphonates cyclohexanones [338]_
prepared
by alkylation
a-copper
reagent
of 335 followed Finally,
[339].
been found to be stereoselective depending
upon the solvent
by acylation
condensations and give
of a subsequently
prepared
of 336 with acetophenone
different
and the presence
carbon-conhave been
diastereoisomers
or absence
of
lithium
of
have 337
bromide [340]_
0
334
333
;
335
Li
(CH3)2N’pl+ph cH3 337
336 N,N-Disubstituted by lithium
amides and N-substituted
dialkylamides
in HMPA, then alkylated
and 339, respectively
[341]_
selenenylated
products
to give
Lithiolactams like
lactams
have also
340 [342].
have been a-lithiated
to afford
species
like
been sulfenylated
338 and
Reaction
of
posed to yield
340
339
338 lithioacetonitrite
intermediate
and retated
compounds with 341 has been pro-
Some chemistry
342 [343j.
of 342 is discussed.
Li+ -tr(C0)3 342 Other tithionitriles sitytated
[348].
have been hydroxylated
and employed in the synthesis
%-Metatated
isocyanides
hydes and ketones
to give
to 345, methanotysis
like
R = hydrogen, like
of which yields
‘and R’ =
343 have also
343 (M = Li,K)
intermediates
pyridyl
,
been condensed
and with carbon disutfide
to give
affording
347 which,
to 346 when M = K,
formamides
to yield
[351]. affords
.
343
344
345
346
347
348
Under the topic like
[352]
348 [353].
M
=c
of miscellaneous
of nitro
lithio-2-nitropropane
nitrosopyrrolidine
Species
3-amino alcohols
upon methytation,
M
the displacement
with alde-
compounds cyctize
Both 344 and 345 have been
345 is converted
with epoxides
[346,347].
[349].
The latter
P-oxazolines.
ultimately
atkytated
have been condensed
344 [350].
In contrast,
trapped with electrophites.
[344,345].
of S-cuparenone
(349)
nitrogen
groups of p-substituted
compounds,
synthetic
nitrobenzenes
in tMPA have been published and 2.5-dialkyl-N-nitrosopyrrolidines
[354].
details
of
by reagents a-Thioethyl-Nhave been syn-
-16 thesized fide
from the lithio-N-nitroso
[355]
and alkyl
of products
arising
halides
compound and ethyl
[356],
respectively.
methoxycarbonyl
Finally,
dtsul-
the wide variety
from dilithio salt 350 and certain acid chlorides, chloro-
acid chlorides, and chloroesters has
been described
[357]. ki
Ph2C-NPh Li
Turning to sulfur-stabilized been conveniently-metalated condense w=ith aldehydes are useful describes
organolithiums.
by LOIPA in THF-HMPAto give and ketones
to afford
in the synthesis
of 1;4-diketones
the use of 353 for
cyclopentanone
of an earlier
method such as low yields
lithium
[360],
(354)
351
of vernolepin
fonates
of primary alcohols
reagent
[363].
Phenylthiomethylhave been used
to afford
of fraudulent
branched-chain
sugars
respectively.
355
354 alkylated
added to 356 to give
fluoroborate
351 which compounds
in which the limitations
355 [361,362]
353
358 [365],
have
Another paper
and cyclcpentenones. formation
have been conveniently
with-tropylium
like
The latter
and n^-phenylthioketones,
352
P-Lithio-1.3-dithianes
sulfides
species
352 [358].
are overcome [359].
and bis(phenylthio)
to prepare a precursor
phenyl vinyl
with arenesul-
357 [364],
condensed
and employed in the synthesis
from certain
ribofuranosides
[366].
OR’
0 356 Monolithiated
s-trithiane.
357 tetrathiocane,
358 and pentathiecane
2, atid 3) have been condensed with carbon dioxide, disulfide
to give
sulfur
‘CH-5/ 2
(n = 1,2,3)
n = 1,
and carbon
360 [367]_
s/(CHrS)o\CHLi 359
(359,
dioxide,
360 (I-I = 1,2,3)
(S02Li,
CS2Li)
Lithiodithiane
361 adds
in a l&fashion
362, a compound
which
subsequently
alder
[368].
Dithiane
reactions
ketones
to give
conveniently
enters
361 also
ketene thioacetals
converted
ii
into
like
CH3
to afford
condensations
The latter
and Diels-
aldehydes
and
compounds are
with NCS or iiBS.
CA
361 Interaction
into Michael
has been added to other
363 [369].
n-haloesters
Si:
to Z-nethoxyacrolein
363
362
of 364 and 365 has been shown to afford (RI- and (S)-4-hydroxyFinally, tris(methylthio}methyllithium (366) has been [370].
2-cyclopentenones
employed in the synthesis
of dl-protolichesterinic
acid
[371].
CH3S
Li CH3SO/
Lithiation
of epoxysulfones
368 [372.373]. stead
Interestingly.
of n-butyllithium
Epoxynitriles
like
367 leads
metalation
to cyclopropyl
cyclobutyl
products
of l,l-dilithio
ii
[379]
have been alkylated
and with epoxides
PhS02XPh
Li2CHSON(CH3)2
like
372 have been converted
371 to a-selenoaldehydes
373 (G = R) by acid chlorides, 373 (G = 0CH3) by methyl chloroformate , and to a-selenoacids
OH) by carbon dioxide ketones
ultimately
and con-
[380].
373 (G = H) by OMF, a-selenoketones esters
[375-3781
Li
370 a-Selenoalkyllithiums
[381].
affords
in-
369 [373].
systems 370 and 371 has been reported
of monolithiosulfones
densed with carbon disulfide
like
369
368
A variety
like
[373].
367 chemistry
derivatives
of 367 with methylmagnesium iodide
or LDIPA affords
behave similarly
Additional [374].
366
365
364
Similar
treatment
a,B-unsaturated
a-seleno373 (G =
of 372 with a,?-unsaturated
epoxides
[382].
4s
I
R” Li
G
RSe%
0 373
372
Methoxyvinyllithium denced by its
reaction
(374)
and 3-hydroxy-2.4-pentanediones lithium
(375)
the first
has
been
A / esters
with
like
halosilsnes
C- or S-alkylated
products
afford
381 is described-
[388]. to yield
Lithium reagents
is observed
to give
to nive
employed [387].
380 with several
epoxides
to
The related
trimethylsilyllithiun
381 [389].
Subsequent chemistry
382 (M = Si.Ge.Sn.
of
and Pb) have been cou-
383 in which retention
of the double
bond
[390]. R3MLi
:M
OLi
n.-.-
HETEROCYCLES Several
large
Lithiosilyl-
have been alkylated
upon the electrophile
has been condensed
olefins
chlorides
alcohols
to the corresponding
379
has been added to cyclohexenones
7.
hydrolysis,
376 to sive
was studied.
by metalation,
depending
Dimethylphenylsilyllithium stereospecifically
/
after
with aldehydes
of the reaction
378
377
Zji n.
[333]
ethoxyvinyl-
0
compounds were converted
and the stereochemistry
configuration
afford,
376 [385]. Li
379 and amides 380, prepared
pled with crotyl
to
as evi-
dihydroxyacetones The related
respectively-
375 377 has been condensed
The latter
378 [386].
chlorides
condensed
to give
OCH3
374 Lithiovinylsilane like
and esters
[384],
stable acylsilanes Li
to b e employed in synthesis
continues
with ketones
papers discussed
number of N-substituted
nicotinic
acid
to determine
derivatives
the extent
certain 1,2-,
aspects
have been treated and position
of dihydropyridines.
1,4- , and 1,6-dihydropyridine
Thus, a and dihydro-
with LDIPA and potassium
of metalation
[391].
Although
t-butoxide
the pyridine
49
derivatives afforded
gave little vinyl
or no metalation,
organolithiums
denced by deuteration Li
like
@yR
p-
c kH3-‘Li 385 1.2-dihydropyridines
384 In contrast, V-unsubstituted and the anbident
pyridines
organometallics
like
alkyl-1.2-dihydropyridines
388 [392]_
involves
with
Incidentally.
the conversion
sized
by alkylation
reduction
The direction
is discussed.
and aryllCthium
of base-cataly
In another
to.afford
and temperature
54ithiouracil
either
derivative process
394 34ethylquinoline THF-HMPAto afford
FM-
p
78
-T \
Li
390 xhich. have been synthe(391)
zed aldol
2,2-bipyridyl
followed
cyclization was treated
392 OF 393 as a function
by Birch of such di-
viith alkyl-
of the stoichiometry
- 393
394 has been found to rearrange
to 395 [396].
rearrangement,
cause of the high electron OSiz
to give
[393].
392
an intramolecular
halides
paper,
to give
of :I-
i395] _
391
went a similar
389 o f 1,5-diketones
of 2-lithiomethyl-Gnethylpyridine
[394].
ketones
electrophiles
a new synthesis
i0p3
388 a series
387 paper described
CH3 386 387 have been I:-
of 389 to 330 by methyllith-
the corresponding ii-alkyl derivatives /- *‘.<, E/' fl ‘I ,-= C .. :;,.A; ci, '\,& :;., ,.' A
. ._st...‘.x Li
like
condensed
ium and heaxing
ii
1
H !
it
i
CH3
A full
compounds
and CR) as evi-
H
-. Y’--‘.H
s-substituted
acid
(R = carboxamides
experiments.
i,H
lithiated
the dihydronicotinic
384-386
Although
dilithiocytosine
density OSiz
397 was stable
for
396 the first
OSiz
397 time using LDIPA in
398 which was condensed with aldehydes. Similar
treatment
via
396 under-
presumably be-
on nitrogen. LiNSiz
395 has been metalated
399 [397].
apparently
dilithioisocytosine
ketones,
and alkyl
of cycloalkenoisoquinolines
400
50 yielded
mostly metalation
when n = 5,6 [398]_
products
In contrast,
401 and little large
or no addition
products
amounts of 402 were realized
402
when n =
398
&-Jy
@qy -4
>i
Li 403 has been metalated
to give 404 [3g9]_
followed
by condensation
Ph
402
401 Tetrahydroisoquinoline kylated
;“’
Metalation
of either
with aldehydes
by n-butyllithiun,
then al-
403 or 404 by sodium hydride
and ketones
afforded
405.
::J-6Jq* ::Jx---qj RA
‘P(OC2H612 // 0
monolithio
(406)
or dilithio
by treatment
two equivalents
of LOIPA in THF/HMPA[400].
afford
a variety
aY 0
Perimidines mostly [401]_
products
405
(407)
may be prepared trophiles
P(OC2H6)2
404
403 Either
// 0
0
like
of 2,3-dinethylquinoxaline
of the parent dimethylated
heterocycle
Subsequent condensations quinoxalines-
of 2,3-substituted CH2Li
o
LCH
with one or with elec-
! ;ycH2Li
T‘f \wlCH2Li
3
406 like 408 react
In one case,
salts
with alkyl
407 and aryllithium
409 which arise
by addition
ring
occurred
lithiation
reagents
of RLi across
to afford
to give
the C=K linkage
410 in low yield.
51
408
409
An unsuccessful bases
like
desired
attempt
phenyllithium
412, mostly
410
411 to 412 via 413 by means of strong
to convert
has been reported
411 was recovered
despite
ArChzlJ
ArC”=llufl 0
by metalation,
cyclized I
is higher
‘C02R
cyclizes in their
by copper(I1)
413 to 415 with or without
presence.
The related
hydrolysis
copper(I1)
non-benzo
sys-
415 acid
but not LDIPA, to give electrophiles
Lithiated
‘C02R
’
fluoride.
4,5-Dihydro-1.3-thiazoli-4-carboxylic
Thus, a full
zn
have been described [403].
414
with various
the
by D20-CD3C02D.
412
prepared
n-butyllithium,
of obtaining
ArCn=f
examples of heterocyclotetraaromatics
salts though the yield tern was also
quenching
rfi
411 Thus, 414,
Instead
0
‘C02R
Additional
[402].
416 oxatolines
to give a-substituted
has been dimetalated
by
Subsequent condensations products
are described.
417 continued
paper described of which affords
(416)
417 [404].
to be extensively
the alkylation
oi chiral
S-o-alkylalkanoic
acids
investigated
in 1976.
system 418 to give 419. 420 in enantiomeric
purity
52 of
45-85% [405].
alkylation
of 418 (R = H) gives
order of introduction yields
sequential
Interestingly,
(S)-(t)-420
of alkyl while
stereoselectivity
(R)-
halide-lithium
cation
entry
dependinq
upon the
nethylation-butylation
affords
to an underside
and two-fold
metalation
acids
For example,
groups.
butylation-methylation
is ascribed
to 418 via initial
either
two-fold
or (S)-
(R)-(-)-420.
Such
of the alkylating
agent
complexation-
Ph
=Q/
RCE
0.. 1 Lie&H3 418
419
Lithiooxazoline nition
418 (R = H) has been found to be capable
towards racemic
mides and iodides
halides
kinetically
in the R enantiomer
enriched
3-alkylalkanoic allows
are
alkyl
acids
(420)
the establishment
Thus, racemic
[406].
resolved
by 418 to give 419 which,
and oxazolines
likewise
enriched
of absolute
of chiral
secondary unreacted
alkyl
upon hydrolysis,
in the R enantiomer.
configurations
of secondary
recog-
al kyl brohalides
afford
The procedure alkyl
halides
and 420 using only 418. Chiral mine if
oxazolines
they might also
[407,408]_ anoic
Butylation
acid
(420)
[407].
of nihutyllithium
technique
of conjugate
containing E4°g]-
serve as suitable of 421 followed
though the authors
the R configuration dition
421 and 422 have been derived
systems
precursors
by hydrolysis
predicted
Conversion and hydrolysis
425 to yield
A,
to optically
the acid
should
gave (S)-f+)-424 has also
methoxyacids
to deteracid
acids
gave (S)-(+)-2-methylhexhave possessed
of 422 to 423 followed
addition-hydrolysis
like
front L-serine
by conjugate
(4081.
ad-
The iatter
been employed on methoxylike
426 and their
q
lactones
‘“=$--9+
CiCH3 421
i)CH3
422
423
Ph
424 Related 428 via
426 oxazoline
429 [410]
responding
2-brnzoyl
by LDIPA to afford oximes [412].
chemistry
included
and the autoxidation derivative
431 and 432;
[411]_
the conversion
of
of
430 by molecular
P-Isoxazolines
427 to thiiranes oxygen to the cor-
have also
the former compounds fragment
been metalated
to a,$unsaturated
R \ \ .. N-
R@-I
427
430
Metalation (436)
isoxazoles
of
and methyl group
on these
(435)
423
429
431
432
433 and 434 by n-butyllithium lithiation
f413].
yielded
In contrast,
Li
both ring-
the use of LDiPA
systems gave only 435.
o-at3
/
433
434
Oxazine deriva:ives
437 and 438 have been found to react
ketones
and aldehydes,
to afford
respectively,
Thus. 437 gave 439 while
437
434
438 afforded
with aldehydes
stereospecifically
to give
[414].
440
439
441 has been lithiated,
and ketones
olefins
440.
438
Thiomethyldithiane
436 with unsymmetrical
esters
then alkylated
or a-hydroxyesters,
or condensed resoectively
[415-J.
1,3-Dithiane-l-oxides have also been metalated and condensed with elecThus, 442 with LDTPAafforded a Z-lithio derivative arisin9 trophiles [416]. from preferential Tithio
salt
by a factor densations
abstraction
with certain of 3-4:l.
of the C-2 equitorial
electrophiles
occurred
Other stereochemical
cis
results
of 443 (R.= CH3 and Ph) with electrophiles_
proton.
Reaction
to the sulfoxide are discussed
for
of this oxygen the con-
6-l
Q
c-Jo
R
H
CH3S
A large of
l urophenes
number of papers appeared lithium
derivatives
of
to allenes
certain
2,5-dialkyl-3-lithio-thiophenes
stituted
thiophenes,
like
containing
additional
selenophenes.
446 [417].
occurs
447 (M = 5 and Se) [418-421]_
ble and do not open [420,421].
chemistry
Similar
andselenophenes
2-chloro
Such ring openings
have been employed in the
446
445
=\_
i
3-halo
compounds have also
of strong three
bases in polar
position
on the sulfur discussed. ford
been described. gives
of the heterocycle
[423].
of the side-chain
dilithiobutadiene
[424].
Condensed
to give
products
without
Thus, treatment
of
of 450 by a variety at the
Products arising from substitution and abstraction of a thiomethyl proton are
452 as evidenced 453,
454.
in which the selenium-
SCH3 450
-\,
the intervention
by condensation and 455 also
has been found to afwith electrophiles open with methyllithium
but not the sulfur-
containing
[4251_
CR3
__-
--KH24,-’
447 (R = SCH3) via metalation
of 451 by n-butyllithium/TMEDA
selenophenes
-=
449
such ring-openings
solvents
Metalation
are cleaved
.-
448
447 of
3-
groups are sta-
&Z-A, Ar
444
examples
sub-
In contrast,
Ar*Ar
other
of
to afford
and 2-dimethylaminomethyl
of 448 to 449 [422]. Li
Several
ringand tel-
444 have been found to open even
445 and ketoacetylenes
vinylacetylenes
lithiothiophenes conversion
in 1976 describing
furans.
_ Thus, 2,5-diaryl-3-lithiofurans
at -65”
%i 443
442
441 openings
Q.
Ph 451
452
rings
55
m
w Other papers
concerned
the rearrangement
gen-metal
with organolithiums of tricyclic
exchange reactions
paration
455
454
453
scribed
y-J---J
of Z-chloro-
and the preparation
and heterocycles
systems
of a variety
like
of dihalothiophenes
and 2-bromotellurophenes and subsequent
have de-
456 to 457 [426],
the halo-
[427],
the pre-
from 2-lithiotellurophene
silylation
of 458 and related
[428],
compounds
CS29] -
R’
R'
ii
457
455
1 . 456
a.
COPPER-LITHIUM Propargylic
461 merely Similar
reactions
than water.
AND 0THER"ATE"
CMPLEXES
459 have been converted
acetates
by running
Intermediate
REAGENTS
the reactions
on propargylic
ate complexes 0
acetals
462 gave ally1
like 464 have been trapped
-
like
463 [431].
by electrophiles
other
-.-R
>
I
R
111
460
459
H-
acetals
460 or
[430].
I‘
R'
R-=
by R2CuLi to either
at -loo and -SO", respectively
= \
oC2H5
462
Methyl propiolate 465 to afford
466 [432],
[433].
Similar
tylenic
ketone [433].
self followed iodides
[434],
have also been
464
463
products
has served
were obtained Related
by condensation and on allenic reported.
as a co-reagent
and to cyclopropyl
of other
electrophiles
ketones
Similar
like
using the latter
additions with
to allenic
cuprates
cuprates
cuprates
468 it-
to give vinyl
mostly
to an allenic
like
and an ace-
on acetylene
like iodine
like 469 to afford
1.2-additions
cuprates
467 to yield
470 [435]
phosphine
56
oxide
have been described
[436].
( *.+C”Li
>=.-\
2
‘P+
2
CuLi
--J
02CH3 467
466
465
=.A*-
cuprates
have also
1437-4391
and with ally1
lustrated
by the conversion
475_
halides
the interaction
Thus, 475 was realized
are il-
472 (R2CuLi) with Z-halo-
474 and addition
[444],
products
G = COR, and !? = methyl [441],
G = COR, and R = cyclopropyl
[442].
but
Similarly,
[443],
X = I, G =
and X = Br, G = C02H or C02CH3. R = methyl
[445].
ALG
A-
have also
476 to olefins
\ 0
0PO(OPh)2 i
476
475
been used to convert
like
477 C4463,
R
I
477
/”
RI
474
473 Dialkylcuprates
J
--Y/G
R
X
479 [447]_
of cuprates
when X = Br, G = COP., R = cyclopropyl
COR. 9 = 2-vinylcyci;propyl
like
acetates
The reactions
olefins.
substitution
when X = Cl,
when X = Cl,
only 474 was realized
esters
to 9ive
compounds 473 to afford
474 was obtained
and n-butyl
[440]
ally1
of 471 to 472 [437].
471 papers discussed
-x,t-unsaturated
been condensed with certain
R
0
Several
470
469
468 Various
enol diphenylphosphate
and ketones
like
478 to ones like
d’ d 478
479
Additional
examples of the condensation
with cyclohexanones alkyllithiums lithium
further
[448].
demonstrate
For example,
di?ithium
add to t-butylcyclohexanone
Reagents
480 also
tion of lithium
to increase
to afford
papers dealing
diphenylcuprate
in the presence
over
and n-butyl-
to -.,S-unsaturated
has been found
1-lrisityl-3-methyl-2-butenone
[449].
carbonyl
the rate of reac-
additions,
of triphenylphosphine;
composed by added ietracyanoethylene
480
reagents
481 in 97% and 86%, respectively_
with conjugate
with
trialkylcuprates of these
tri-n-butylcuprate
have been added in a 1,4-fashion
In other
compounds.
of dilithium
the superiority
the cupraie
is,
however,
Lithium dinethylcuprate
de-
has heen
condensed with pyranosides like 482 to a fford 453 [450], and with oxo-enones like 484 to give 485 via regiospecific intramolecular aldol condensations [451]. OH
R”@ro _
&R
”
H
480
481
482
484
485
CH3 483 Lithium cuprates furan to alcohols to sulfoxides
[453]_
regioselectively
have been found to cleave
486 {P,’ = H or CH3) [452], Lithium dimethylcuprate
added to iron
salts
THF and 2_methylte:rahydro-
and to convert
sulfinate
esters
has been stereospecifically
487 to yield
and
488 14541.
cH3
Lithium cuprates natural
products
spirovetivanes lide
were employed as part of the synthesis
in 1976 including [456],
14611.
dl-sesquicarene [463],
alkylated
recifei
side
organoborates,
on the B-carbon
[457-4591,
[460],
and dl-sirenin
and the acyclic
Turning to lithium
methyl jasmonate
prostaglandins
from Cephalosporium
cockroach
488
487
486
certain [462],
of a variety
and related
a naturally
of
compounds [455],
occurring
macro-
a-methylene-y-butyrolactones
a sex pheromone of the German
chain of several natural products [464]. a 1kynyl trial kyl borates 489 have been
by methyl sulfate,
triethyloxonium
fluoroborate,
and
58
other
active
alkyl
like 49? [455].
halides
and nitriles,
ters, tones,
y-ketonitriles,
y-ketoesters, acid
idation
Details
[467].
instead
upon hydrolysis l_i+
R3B-C-CR’
c=c
/
489
tylenes.
Similar
ployed
to synthesize
been studied prostaglandins
0
[466].
412 after
,YL I!
491
rearrangements
carbon
conjugated _
have been em-
borate
for
494 and with the
reagents
has
the synthesis
(Sia)
of
2_
c:ck*
C-CR’
494
Reagent 489 has been condensed (R” = Sn(n-C41fg)3)which, The use of other chloride
electrophiles apparently
495
with tri-n-butyltin
upon treatment
with formic like
yielded
chloride acid,
to give
affords
trimethylaluminum
491)
Z-olefins
chloride
490 and an isomer since
and
hydrolysis
of Z- and E-olefins.
Z-Brono-6-lithiopyridine afford
ace-
E471.4721.
493
gave mixtures
493 whic$ allyls,
acetylides
( G+
[473].
salts
unsymmetrical
of other
of such reactions
R3B-CX-Li
phenylsulfenyl
492
Intermediates
lithium
Iodination
suitability
R’
= alkyls.
and of 495 [470] diynes.
of appropriate
alkynyldialkylboranes
489 (R’
then affords
of 494 [469]
by condensation
to determine
to give
iodination
unsymmetrical
ox-
of 490 to 2 or E-
R”
Subsequent
es-
1,4-dike-
The use of
to ketones
R’
it
at the acetylenic [468]_
ketones
acids.
490
undergo alkylation
495 were prepared
leads
yield
489 (R’ = H) have been converted to dilithio
Boron reagents trimethylsilyl)
gives
by =-haloketones,
about the conversion
/R’ \
oxidation,
bromide to ultimately halides
by carboxylic R,
after
been alkylated
and y-ketoalkynes
of alkyl
are provided
R2B
corresponding
490 which,
and by a propargylic
methanesulfonic olefins
to afford
Reagents 489 have also
intermediates
tic
acid
treatment
for
the preparation
like
has been added to trialkylboranes 496 which decompose to vinylboranes
of 497 to give
498 illustrates
the utility
to presumably 497 [474].
Ace-
of the method
of pentadienenitriles. N
R2+ s+L CN
BR2
496
h
497
H
H
498
H
59
Trialkylboranes
have also
afford
499 which,
upon treatment
been condensed
idstion
of 500 then yields Li+ :!
with a-methoxyvinyllithium
with hydrochloric
acid,
dialkylmethylmethanols FI
gives
501.
Y
R-81
OCH3
The course treatment affords
of hydrolysis
503 and 504,
respectively_
The boron of several replacement (R”‘X:
iodide
addition ethanes
vinylsilanes
[475],
borate
complexes
synthetically
useful
R” = CH3) followed
and benzvl
Similar halides
505 quent treatment
replacement
yields
by copper such
Thus,
of alkyl
halides
on 506 follonied
507 [478]
and 1,2-diarvl-
chloride
and basic
hydrogen peroxide
Subseaffords
510. SPh f R’ 30-C-R I SPh
Li RC(SPh)2
510
509
508
Yionane ate complex 511 has now been found and epoxides
/U
II/-
506 507 have been condensed with SOS to give 509 [430].
with mercuric
alcohols
is converted
511 in the presence
of methanol and lithium
Reagent 511 al.so reduces
to cis-
aldehydes
between isomeric
capable
of reducing
In the former case,
14821 to alcohols.
methylcyclohexanone
discriminates
acid
respectively_
irialkylboranes
[481]
has been replaced intermediates.
by the addition
(R3BCii3)-Li’
secondary
fhus,
and aqueotis hydrochloric
hydroxide
505 [477]_
of acrylonitrile
501
502 depends upon the pH [476].
nther examples are described_
lithium
to give
on 502 (!? = Sis,
affords
R
of borate
of 502 with aqueous sodium
using cuprous
&
/i
O/CH, 5 530
393
ox-
OH
. -., .Y iJ=
to
5CKl[475]_
ketones
example,
and trans-4-methylcyclohexanol
selectively
ketones
for
like
methoxide,
respectively
in the presence Z- and 4-heptanones
4by
[481].
of ketones, [481],
and
by
60
-reduces
aromatic
and aliphatic
tions,
respectively
[482].
epoxides
act-l-y1
chloride
systems like
ketones with lithium
oosi-
such reductions
formed by reaction
of cis-bicyclo[3.3.0]-
512 in 1976 describing stereoselective trisiamylborohydride
with triethylborohydride
[435]_
[484], The latter
513 reductions of cyclic
and reductions reactions
of alkyl
are useful
tosyl-
in the
of alcohols_
deoxygenation
Aluminum ate complexes 514 (R = Sii) silanes
and used in the synthesis
hindered
after
513.
x 511 Reports appeared a:es
remaining
It has been conveniently
has been shown to be 512 [483]. of 511 with acetyl
at the most and least
The organoborane
continued
with methyllithium
515 [486,487].
to be investigated_
followed
Other alkylations
by alkyl
Thus,
halides
were also
[487.488]_
reactions
leads
The use of epoxides
to ally1
alcohols
R’
R
instead
on compounds 514
sSi
nun, and lithium
in such
R’ /R’
OH
515 517 has been prepared
in the presence
LiA1(SiZ)4
R3
H
R’
514 alanate
substituted
halides
of alkyl
R “I ,-I-I
Finally,
afford
516 [489].
/ (i-C4Hg)2Al
of
(R-X) gave vinyl-
effected
where R = phenyl , butyl , and hydrogen to stereospecifically ethylenes
treatment
516
517
from chlorotrimethylsilane,
alumi-
of mercury [4901_
LITHIUM-HALOGEN EXCHANGE REACTIONS
9.
A variety derivatives [491]_
of o-haloarylimines
by n-butyllithium,
Hydrolysis
518 have been converted thencoupledto
of 519 gave dialdehydes
to their
519 by various
copper
o-lithio reagents
520_
R
518 Low temperature
‘sHllN
d 519
halogen-metal
exchanges
520
on isomeric
bromobenzoic
acids
and derivatives continued to be described in 1976. Thus, o-bromobenzoic acid wds converted to its dilithio salt 521 and condensed with ketones to afford
61
spiro
systems like
525 [495]
522 [492].
were similarly
Lithio
prepared
derivatives
523 [493],
524 [4?4],
and condensed with a varietv
and
of electro-
phiies.
522 R
521
523
c:i
ii 526 525 dibromo526 has been formed from the corresoonding
524 Cyclobutabenzyne bromoiodoaromatics
by treatment
trapped with furan or allowed present
in the reactions
and lithium certain
of
with n-butyllithium to dimerize.
diphenylarsenide
[497],
“Umpolung” reagents of the corresponding sation
for
with lithium
quinones
o-silylarylamines
like
gave derivatives
by reactidn and vinyl
of alkyllithiums bromides
treatment
Simple conden-
528
reagents [5013_
[SO33 have been prepared
by treatment
14991.
528.
527 Alkenyllithium
with
[498].
527 have been prepared
bromo compounds with n-butyllithium
with electrophiles
were also
diphenylphosphide
and were employed in condensations
to afford
and
Benzyne 526 was .
Genzyneintermediates
1,2-dibromobenzene
silyimethyldialkylamines
[496].
like
529 have been prepared
at low temperature Polyhalovinyllithiums
similarly
of 532 (R = aryl)
stereospeiifically
with vinyl like
by lithium-chlorine
with organolithiums
affords
iodides
[SOO]
530 [502,503]
and 531 In contrast,
exchange. lithium
arylacetylides
[5023.
R\
H
RA
Li 529
Other linsaturated included give
F
Cl
FH
ii
530 lithium reagents
533 which condenses
# Cb
in the synthesis
aldehydes
-F
R
-Li
FH
Cl 1 532
531 prepared
with carbonyl
c-methoxy-a.E-unsaturated
which is useful
F
by metai-halogen
exchange have
containing compcunds to ultimately (534) [504] , cyclooctatetraenyllithium
of bicycle-octatetraenyl
[SOS],
and various
lithium
acetylides
534‘made from l-haloacetylenes
and n-butyllithiun
[5D6].
OCH3 r./~~‘-__
---2
Li
Li 533
534
In the area of saturated converted
to benzyllithium
dibromide
to give
similarly_ lithium
halogen
compounds,
o-bromobenzyl
537 by n-butyllithium;
a bibenzyl
On the other
535
derivative
hand, o-bromobenzyl
536 couples o-Iodobenzyl
[507].
chloride
539 which has been condensed with a variety
Eromophenyl )ethyl lithium
bronide
536 is
with starting bromide behaves
538 is converted
to ary?-
of electrophiles.
bromide and y- (o-bromophenylIcthy1
chloride
also
-f-(0afford
arvl-
derivatives-
536
and trans.-iodotosylates
given
the corresponding
tally
[508].
an unrelated
Similar paper,
lithium
results certain
of dibromo orecursors
539
538
537
Treatment of cis-
reagents
klhich cyclize
were obtained rotanes
540 Gth
like
n-butyllithium
has
to 541 stereospecifi-
on the corresponding
542 have been prepared
4-enes.
In
by reaction
1ike 543 with ohenvll ithium f509].
\I:t
541
540 Finally, to carbenes
dichloro
derivatives
er
have been converted
Cl
XEOUCTIORS ADD RADICALADIOI15 A review article
asxnonia solutions tion
543
by methyllithium. Cl-,
lo_
542 544 [SlO] and 545 [Sll]
, D&a
dealing
and related
with reduction
of heterocyclic
reagents
arrived
to its
tetrahydro
too late
compounds by metal-
for
inclusion
in Sec.-
derivatives
546-548
in amnon-
t [512]. The reduction
of biphenyl
63
ia has been studied of 546.548 Possible
cis-
fected
of anthracene
and trans.-549.
yielded
Reduction dihydro
[514].
increased The latter
of fluorene 552
compounds arose
constitute
disilylated
For example,
short
Reductive
from metalation
amount
methylation
of
alcohol
a simple
synthesis
acid
periods
gave
tetrahydro
of fluorene
rea-
lithium,
mostly products
with lithium/-
and 9,9-dimethyl
of the 9-hydrogen
553 E ring of yohimbane 555 has been converted
of o-methoxybenzoic
benzene,
in ammonia for The small
an-
of silylatins
550 and 551.
554 and o-methyl-
by lithium/arrmonia/i-propyl reductions
corresponding
of i49 was ef-
in THF affords
[516]_
time.
bromide afforded
and sodium in THF has
Dehydrogenation
in the presence
[515].
by lithium
and 553
with increasing
552 The aromatic
the
afford
of benzene derivatives silylhydroaromatics
derivatives
ammonia/methyl
(556)
and 39% with magnesium.
in ether/benzene
respectively
i thium/TMEDA to
Qeduction
also
by lithium
and 1,3-dichlorotetramethyldisiloxane
ilar
The combined yields
the metal [513].
12.5:: with sodium,
were 18: with lithium,
by n-butyll
tracene. gents
of
mechanisms are discussed.
Reduction given
as a function
folloued
554 to a cyclohexanone
by aqueous acid
in the presence
of Z-alkylcyclohexenones
derivatives. atoms of the oarent
of alkyl
557 [518].
[517]. halides
Sim(9X)
64
H02C’
I .; OCH3 557
Improved 559,
procedures
respectively,
for
involving
the
conversion
the
use of
of
indole
ester
has been
ring opening,
and ring
reclosure
with liihium/aEzeonia/alcohols 563
used to remove the phenolic
from e’-tetrahydrocannabinol
been employed to reduce 3-furoic
aIS.
[522]_
The overall
to a butyryl
Reductive
boxyl
hydroxyl group pasked Lithiuc/azmonia has
[SO].
to 560 and 561 via E-elimination,
Thiophenes
to afford,
sequence
after
represents
like
562 have been treated
hydrolysis,
aninoketones
the transformation
like
of a thiophene
methylation
563
562
of 564 and its
gave 565 and 566, respectively group controlled
group was introduced group.
acid
[521].
561
try of the 9-carboxyl methy
pub-
group.
560
methy? iodide
558 and been
559
558 Lithiun/amonia
to have
H
H
as a phosphite
and carbazole
fithium/armonia/r!!ethanol
epimer by lithium [523].
that of methylation
from the side
in THF followed
Clearly,
of the molecule
by
the stereochemis-
at C-8 since opposite
the
the car-
C02H
‘CH3
Menthone (567)-isonenthone tively
to menthol
Other reducing
566
565
564 (568)
mixtures
(5G9) and neomenthol
media and hydrogen
(570)
including
systems studied,
in the presence
have been reduced stereoselec-
only
by lithium/ar;mocia
sodium and potassium
of ruthenium,
rhodium,
[524].
in various
and platinum,
were
not stereospecific.
iin +:-unsaturated duced
of
IO-epieudesmane
bromide to afford,
among other
from C-alkylation, of
like
ketones
and a tetrahydrofuran
intermedeo:
has been reductively
572 has been converted
the presence
an epoxide.
570
or lithium/ethylenediamine
sesquiterpenes
Methyl benzoate
ter
ketone,
by lithium/ammonia
propiophenone
569
568
567
have been re-
as part of the synthesis [525].
ethylated
by lithiun?ar;monia/ethyl
ethyl henzyl ether from 0-alkylation. products, and 571 from ring reduction [526]_ Ally1 es-
to allyllithium
to qive -i-alcohols
CH3Cil
reagent
573 by lithium
in THF in
r527]. _ Li+
‘\L ’
K’
‘\,
!
‘H
571 Tandem alkylation-reduction cyclopropyl sequence
aromatic
hydrocarbons
572 has now been applied [528].
The process
573 to the synthesis is illustrated
574 to 576. 0
OLi
574
575
576
of a-
by the
66 Related
to the above,
by lithium/amnonia the presence
cyclopropyl
phenyl ketone has been reduced
Subsequent
[529].
of amnonium chloride
reduction
to 577
of 577 by lithiumfamnonia
and sodium benzoate
affords
in
578 and 579,
re-
spectively. OH
OLi
I.
In contrast. [532]
cyclopropyl
are cleaved
the cyclopropyl
ring
The conversion
tion.
reduction
of
several
chloride
tions
the cis
530 [530,531] like
and 531
532 and 533, re-
several
organic
halides
to organolithiums
(and bromide)
other
products
534 was converted
in which
are presumed to have proceeded
tion
of 587 with n-butyllithium
tion
of configuration_
(587)
and heptenes
and trans hydrocarbons
reaction
with lithium
was not stereospecific
were obtained
via vinylic
[533].
[534].
in TtiF to since Such reduc-
radicals.
gave the respective
2
men-
586
585 reagents
deserves
to the lithium
536 via a cyclization
of E- and Z-4-chloro-3-heptenes
the vinyllithium of
products
yielded
then condensed with 525 to give
Reaction mixtures
to give
also
584 afford
in compounds like
has been opened.
Thus, allenyl
reagent,
rings
by lithium/ammonia
The latter
spectively.
579
57.3
577
In contrast, reacvinyllithiums with reten-
-‘\ 587
Lithium/awonia stead of the desired an electrochemical
reduction propellane process-
of 588 gave mostly 589 [535].
Similar
norbornane results
and a dimer inwere obtained
by
6i
589
588 ,+ChJoroenamines
590 have been converted
magnesium in solvents reaction
like
with deuterium
oxide
enanine 594 was observed
59G Various :Lnitrosamines
by lithium
bonds have been cleaved as illustrated r. --\
by radical
alkyl
ium instead
and ethyl
iodide
potassium
The C-alkylations than by nucleophilic
56
‘SH13
of adducts
afford
with alkyl
and the solvent
are said
halides [540].
598 and 599 (ortho
and cesium ketyls to occur
give
via initial
[gJq” 599
and para)
to all
to the use of
have been studied
600
Jith-
as-
the lithium
but no 600 or 601. of these products.
electron-transfer
)Af
to alkyllithiums from 597 and the
For example,
and para)
rise
displacement_ 0
(ortho
References p
i -\
converted
j.
$)-);I
(
L-I
ketyls
Carbonby Jithium/-
of 595 to 596 [538].
derived
cation
593 secondary
[5373.
contamination
of benzophenone
R2?r-\
in good yields
596 have been quantitatively
595 chlorides
of the alkali
In contrast,
)i-i/
[539]_ The success of the method is ascribed of sodium and to the steric bulk of 597_
Reactions a function
hR2
?,R ‘2
hydrocarbons
and
after
Deuterated
592, H=H 594, H = D to the corresponding
‘*-C6HJ3
anion 597 without
alkyllithiums
593.
and magnesium in ether
to give
by the conversion SeCH3 Xyl
‘L,’
Various
_(
>
591 have been cleaved
amines in very low yields
ketyl
were enamine 592 and diner
\.-iLi /; \ hR2
2
ethylamine
sodium,
The major products
with sodium and magnesium only. H
>;;;c:,
sefenium
to 591 by lithium,
THF and hexane [536].
steps
,;a 601
rather
Overreduction tyienic kali
ketones
metals
has now been avoided
like
in liquid to azo/-
of steroidal
naphthalenes
Lithium naphthalene
ammonia [541].
in a new synthesis
ployed
nitrobenzene
in the cvclization
602 to 603 by using alkali
of (?)-sempervirol
instead
has also
aceof al-
been em-
15421 and in the reduction
of
and__azoxybenzenes [543]. -./. .t>
_/-
-J1
_ ..I,+
t 111
, i .---
IA/
‘\ aH 603
602 ll_
REACTIONSWITH INORGANIC Several
like
AR0
I-cyanocarboranes
and m-carboranes
ORGANOMETALLIC
COMPOUNOS
have been prepared
with phenylcyanate
604 have been synthesized
[545].
of 606 with n-butyllithiom
by reacting
605 with certain
rivatives
papers appeared
carboranes
(8lOHl2)pdjphenan) 606
in 1976 describing
of germanium, tin, compounds [547]
the preparation
Carbanion
607 [547,548].
and lead to give and benzyl
and reactions
607 has been condensed
608 [547].
bromide [548],
Reactions
and of lithium
of de-
of 608 are discussed_
608
607 Other boron-containing methoxyboron chloride.
molecules
lithium,
prepared
and silicon
using
SiCMOCH3),14
into
the details dilithioalkanes
except of
[SSO].
610
611
metals,
layered
and Ta. X = 5, Se, and Te [551]. cases
n-butyllithium
and titanium
has been employed to
MX2 compounds where M = Ti, A limiting
VSe2 which gave Li2VSe2.
the preparation
and 610 from
CH3-0-CBIOHIOCLi
In the area of transition lithium
were 609 from di-
[549]
(Cii3-~-CB10H10C)3P
609
intercalate
lithium
tetrachloride
611 and bis(methyl-o-carboranyl)chlorophosphine
in all
lithium
605
bis(boryl)methide
607 with carbonyl
o-
complexes
606 has been made by treatment
(Ph3P)21r(CO)Cl
604
with derivatives
C-lithium
iridium(I)
in THF [546].
(Ph3P)21r(CO)(c-carb)
Two full
by condensing
New stable
[544].
An anion of phenanthroline-containing
of lithium
.i
composition A full
of titanium(IV) dichlorides
[f&G?].
Zr.
Hf. V, Nb,
of LiMX2 was obtained
paper appeared describing
metallocycloes.
like
The characterization
612 from and
69
reactions
of
prepared
the metallocycles
from alkyllithiums
dicyclopentadienylzirconium methylzirconium
(613)
Other compounds in this
is discussed. included
and hafnium dicarbonyls and zirconium(W)
[555],
[554],
614 [556].
*p3
lithium
pounds similarly lun [559],
prepared
I t-
1
CH3 -2
615 have been prepared
and niobium(V)chlor
include
hexacoordinated
_i
I
614
compounds like
cyclopentadienes
y3
! Zr (ii--fi+O
613
Cyclopentadienylniobium tuted
[553],
bis(fluorenyl)di-
amides like
(C13H9)2Zr(CH3)2
612
family
tetrakis(pentafluorophenyl).zirconium
from- substi-
[557,558]_
pentamethylniobium
[559],
tantalum complex 616 [560],
Other com-
pentamethyltanta-
and tetamesityl
com-
pounds 617 (M = V, Cr) [561,562]. ,CH3 (CH3-@&--+~Li 3 617
616 615 Carbene complex 618 has been synthesized reagents,
phenyllithium,
then trimethyloxonium
complex 619 has been prepared and lithium
cyclopentadiene
hexacarbonyl
, lithium
ium and tungsten species
like
/
--ArCr(C0)2(C
\
[564].
and triethyloxonium
621 have been condensed
action
fluotoborate
reagent
chromium
[565]_
Chrom-
with organ01 i thiums to give
0CH3
I Ph
/OCH3
.OCH
)
(CO)5Cr(C$Ph
(co)5w=/il \ Ph
3,
Ph 622 more papers appeared discussing
of molybdenum and tungsten Thus,
full
with molybdenum(II1) to afford
from
619
621 Several ple bonds.
Carbyne
and 623 [567]_
‘Ph
properties
[563].
tungsten-bromine
Compound 620 was prepared
618
(CO)$l(C
fluoroborate
from the corresponding
dithiane,
complexes
622 [566]
from ?-aryltricarbonylchromium
625 [569]
papers describe chloride
to give
and 626 [570].
of 626 with methyllithium
623 structure,
the preparation,
compounds comtaining the reactions 624 [568]
metal-metal
of lithium
yields
dial_kylamides
and with tungsten(IV)
Other examples are cited. 627 [571].
A related
and multichloride
In addition, condensation
reof
i0
anti-626 tion
with lithiomethyltrimethylsilane
of configuration
at tungsten
Mo2(NlMe2)6
U2(NMe2)6
has been shown to occur
via a bimolecular
four-center
with retenmechanism 15721.
(Et211-7%
H2C12(NEt2)4
CH3
Dihydrides the latter acid
reacts
chlorides,
627
626
625
624
to give tetramer 629; 628 (El = MO, H) react with n-butyllithium at the transition metal with alkyl halides, as a nucleophile esters,
and benzaldehyde
to afford
metal-carbon
systems
like
63D [5731_ n5-cp
n5 -cp
Y.M/H
3 -Cp’
?;_C/
H
’
‘5
((C5Hg12MHLi14
Other chemistry
in this
631 from hexamethyltungsten more fluorines phenyilithium
family
included
the preparation
and methyllithium
of 632 by organolithiums across
and tertiary
630
629
628
the azo linkage
[574],
[575],
of tungstate
the replacement
the stereospecific
of 633 [576],
and I-arylation
of
of ethers
PhHC16Li
633
632 Manganese compounds 635 fR = CH3, Ph), lithium
with 636, represent
carbene
is stabilized
complex (637)
carbene
as a ligand
has been obtained
/
complexes
634
prepared
by reaction
where a dialkyl-
to a metal atom [578]. similarly
MO calculations
C5H5(C0j2Re=C \
have been performed
that these
of nucleophilic reactions
at coordinated
on 638 and 639 to determine
attack
are frontier
rhenium
CH3
637
636
the site
of methylor arylalkyl-
An analogous
3 635
-
[579]_
C5H5(C0)2MnXR
C5H5(CO)2Mn=C
that attack
of one or
amines by 634 [577]_
631
.cluded
ion
addition
[CsH5Mo(C0)2?W]PF6
control
‘P .
on such species rather
CO is much more likely
[580].
factors
than charge controlled for the acyl
which
It is conspecies
and (639)
‘71 than for
the carbene
condensed Protonation cule
complex
(638).
Experimentally,
with 640 and 641 at CO to give of 643 afforded
the enol
642 [581]
methyllithium
has been
and 643 [SSZ],
respectively.
tautomer of a metalloacetylacetone
mole-
[582]. OCH3
/ (COJ5CrC
0 (CO)5F!n/K
“ii
(COj5Rn /Y
?
Ph
3
638
639
64’3
-_: (COj5Ze/-\ 642 The first thesized
acylsilane
derivative
of a transition
from 655 and triphenylsilyllithiun
metal,
644,
has been syn-
[583]_
; (C0)3jP)2ReN
(CO),Qe(P,)
‘SiPh3
644 Other rhenium and manganese compounds prepared dirhenate(III)
(646)
cctamethylrhenate(Yif and allenylidene
fron methyllithium
_
645 in 1976 include
and rhenium pentachloride
(64E) fro:n methyllithium
octamethylor 647 [5%].
and hexanethylrheniun
compound 649 from t-butyllithium
and acetylene
[535],
complex 650
[5863. Li2Xe2(CH,), JO
Li2Re(CH3)8
Re,(KPh),Cl2
646
648
647
649
650 * ferrate
Lithiuncycloheptatrienyltricarbony~ various
metal
carbonyl
halides
to aive
Mn, Re. X = 3 and 14 = Rh, X = 2)
verted
to bisffulvalene)diiron
ferrocenes prepared
[589]
[587]_
(654)
(651)
has been reacted
hetero4inetallic
complexes
Dilithiofulvalene
by iron(I1)
chloride
(653)
by treatment
of appropriate
lithium
has heen con-
[588].
and 1,1’,2,2’,0,4’-hexakistrimethylferrocene cyclopentadienes
with
652 (M =
[590] with
Polymethvlhave been iron
72
bromide and chloride,
respectively.
(C7H7)Fe(CO)3Li 652
651
653 654 Two related been prepared [591]
bis(cyclooctadiene)cobaltlithium
from 1,5-cyclooctadiene(cyclooctenyl)cobalt
and from cobaltocene Iridium
respectively. responding ophilic
iridium
nea protecting
and lithium
complexes
chloride
reactions
of
like
group for
and aryllithiuns
peptide
ethylene
[593].
syntheses
complexes
alkylphosphine,
657
with ;-MO-C bonding,
reaction
and ethylene
affords
illustrated
of this
same nickel
compounds like
reagent,
[Li(THF)4]C[Ph2P
dinitrogen-nickel
in ether
phenylsodium
nickel
[SSS].
di-
Xi(C2H4)2
/ \_
?iI (C2QZ1-
complex 660 has been prepared
phenyllithium.
by reaction
with phenyllithium/phenylsodium
Ethylenebis(phenyllithium)nickel
compound have been synthesized
reagent.
lithium
659
all-rrans-1.5.9-cyclododecatrienenickel nitrogen
have
TYEOA, and
659 [597].
658 “Side-on”
by 658, (RLi),
organolithiuns
[Li (2T?lEDA)]+[PhNi (C2H4)2]-
nucle-
for a
(CO)Ir(Ar)(PPh3)2
(C8H12)2CoLi(THF)x
Similarly,
[596].
Two papers described as model reactions
656 (0)
[592],
from the cnr-
[59$.595]_
from bis(cyclooctadienyl)nickel,
been prepared
of cyclooctadiene
657 have been synthesized
655 nickel
and phenyllithiun
in the oresence
lithium-cobalt-phthalocyanines
(C,H12)2CoLi(LiPh)-2(C2H5)20
hovel
compounds 655 and 656 have
phenylsodium.
and the
by reaction
of
and ethylene
of
and
related
the same triene-
[599].
660 Other compounds in this bony1 dianions
like
family
661 by reduction
recently
described
of platinum
include
chloride
platinum
car-
systems or pre-
'73
formed platinum
carbonyl
from the corresponding kel chloride
systems by lithium chlorides
from a complexed
and metallocycles
[602],
nickel(II)
like
[600],
platinum
complexes
and perfluorophenyllithiun chloride
[61)1],
and lithium
663 from the platinum
chloride
like
662
benzylnic-
tribenzyltin and 1,4-dilithio-
butane [603] _ Pt3(CO)6Li2
A variety
of
thorium derivatives
664 (R = alkyl
pared by reaction
of the thorium chloride
Grignard
[604].
reagents
663
662
661
Ring-bridged
and alkenyl)
derivative
have been pre-
with organolithiums
uranium halides
and
665 have similarly
CG(C5H4)212U2C15Li (THF12
(qs-C5Hs)3ThR
aJGbJ Lit
665
664
666
Li+
Terbium and holnium compounds 667 (R = t-C4H9) have been synthesized the reaction prepared
of 668 and lithium
by the interaction
di-t-butylphosphide
[606].
of 670 with n-butyllithium Ln(=>?<
667
663
The first
organogold(I)
pared by reaction
complex containin
of perfluorophenyllithiua
tetrasilane
673 may be prepared
I,Cl3
670 a S-donor.
671.
has been pre-
and 672 [6g!?].
metal.
Table,
by treatment
[609].
This same paper describes
with lithium
P’,
672
tetrachloroplatinate
sink.
Ln[-
ClAuSC4Ha
Turning to Group IV of the Periodic
lithium
from
669 has been
[607]_
669
671
potassium
Ylide
)3
(C6F5)A~SC4H3
cyclopentasilane
been
of 666 (G = Cti2, Si Z, n-propyl ) wi.th uraniun( IV) chloride
made by condensation [605] _
The latter cleavage
it has been found that perarylof either reagent reactions
674 or 675 with is said
to act as a
of perarylcyclo-
p\siPh Ph\
--,*ilPh
_‘-
p/-S’i
I
\Pil
‘+Ph Ph
ph5si?h
674
673
Other preparations
of cyclic
silicon-containing
by 676 from 1,8_dilithionaphthalene 6T8 and disilane
ylide
conpoun-!s
are
and dialkyldichlorosilanes
679 16111,
illustrated
[610],
677 fron
and 680 from 681 and dic5lorodinethylsilane
[6121_
(CH3)3P
(CH3)3P
676
677
678
680
681
CH 13 Cl,Si\
; C12Si/
1
CH 3 679 Divalent or,
species
682 (M = Ge. Sn. Pb) have been prepared
from 683 and 684,
s*hen X = Sn or Pb, from 683 and MC12 [613,6147. ZS-
Fi
Sir
ZSi
,Siz J--+l-_(;
‘>-( ZSi
‘\
> _Sl
Sis
682
683
Imidazolidinonederivative aprotic
solvent
reactions
metal to give
that 685 lies
684
685 has been tested
for organometallic
with ketones and lithium It is concluded
‘Sis
for
by reacting
disilyated
its
suitability
as an
chlorotrimethylsilane
derivatives
like
between THF and HVPA in promoting
686 [615].
such reactions.
i5
Other chemistry reagents
the preparation
in this
across
L-6171, the synthesis chloride
group included
the addition
of of
tin
triphenylsilyllithium
lithium
using get-manium(!:‘)
of organolithiums
linkag..e of :-germyl
the nitrile
of 683 from the correspoxding
and the conversion
‘*i_
686
685
Grignard
/Xii:
0
-CH3
nitriles
reagent
and
687 [616],
by trans.-netalation
from 689 and methyllithium
cyclopentadiene
[618],
to cyclopentadienylget-manium
tri-
chloride [619]_ :Si
3EeCH2CC
(C2H5)
like
(CO)4CoSiPh3 l-i
687
688
An interesting derivative fected
691 and dichlorodimethylsilane
using
SilSiCl3
689
690 has been obtained
dispirotetrasilazane
The synthesis
[629].
and n-butyllithium
from tetralithio
followed
by addition
of 691 was efof aniline,
then
more n-butyllithium.
691
690
Treatment of silicon-nitrogen cyclic afforded 622]_ yielded
systems_
693a-b apparently In contrast,
694 presumably metalation
to be prepared
Rcferemesp.58
R’
= Ph)
via methanide migration
692c (R = i-C-&.
695 with n-butyllithium similar
systems 692a-c
Thus. 692a (R = t-C,H,.
via a silicenium
and 692b
ion [622].
gave 696 via the latter
(R = R’
to a silicenium
R’ = Ph) with the
of 697 gave only N-lithiation,
[624].
with n-butyllithiun
smaller
Reaction
route
[623].
the first
also
gave
= t-C4Hg)
ylide
i-propyl
of silyl On the
[621, grouo
system oth
hand,
such organometallic
76
t-c&,
Y
:
Si-R’
I
I
X--
Zi-N-:i-NHt-C4Hg
; Si-
I= 692a
R’=Ph)
(R=t-C4H9.
692b
(R=R’=t-C4H9)
692~
(R=i-C3H7.
i-C3H7\
p3 N-
IiHt-C4H9 YPh
I
i
TSiL
N-t-C4Hg
694
693a
(R’=Ph)
693b
(R’=t-C4H9)
R’=Ph)
(t-C4H9)2Si,
AF NHt-C4H9
Azosilolines
like
and phenyllithium
697
696
695
698 have
been
synthesized
from
J.
Silylated ate
ter
aldimines
complexes
enamino-tin yields
chlorotributyltin
halides
may now be simply
[626,627] system,
previoulsy 16291.
Zi-N=CHR
with for
described Similarly,
prepared
by treatment
chlorotrimethyl_silane
example,
702-703,
by treating metalloimines
[628].
of The
can be obtained
iminolithium 704 have
in
reagents
bet-
with
been obtained
M+(C2HS)3B-N=CHR
from jR \
CH3--=-N
702
701
Ph
Lit
-YNR 703
new imino-
[6301.
700
SnR3
699
699 (700)
701
metalotropic than
705 and metal
precursors
_Ai_ _/’ - NHR
698
boron
benzyne
[625].
Ph
Ph 704
705
SnR’3
ii Nitrogen-nitrogen with lithium
and Group IV systems.
tetrachloride, reaction
and nitrogen-oxygen
and butyllithium
Thus, reaction
affords
708 L-632]_
have been synthesized Finally,
Several
bis(trimethylsilyl)hydroxylamines n-butyllithium,
(Si)
NOSiz
lithium
phosphinelithium like
like
followed
708 / PhN 1.
OSis
Sir
711
712 have been prepared
by addition
of
by reduction
chlorotrimethylsilane
compound 713 has been synthesized
n-butyllithium
from
[634].
710
Organosilylphosphines
709
[633].
have been prepared
ZiNHOSiz
709
with
(711)
gives
like
and chlorosilanes
707
2
Similar
then hexachloroethane
and chlorotrimethlsilane
706
carbon
707 [631].
tris(organosilyl)hydroxylamines
from 710, n-butyllithium,
phenylhydroxylanine,
been combined
of 706 (M = Si),
aminoisocyanide
of 706 (M = Ge) with an organolithium,
germyldiimine
phines
systems have also
of phos[635].
Silyl-
from 714 and organolithiums
[636].
(Zii)3P
Calculations complexes states these
have been performed
[637] _ The authors
on the activation
conclude
in which the N-N bond is highly states
can be described-as
of nitrogen
in n-iinN
that stabilization
of the electronic
loosened
and that certain
occurring
can occur
from one- or two-electron
of
reduction
of nitrogen_ Diazadiphosphetidines phenyllithium
traphenylphosphonium dialkylamides, or the formation group.
like
715 have been prepared
Phosphineimines
[638].
chloride
though,
affords
like
and lithium
alkylamides
homolytic
decomposition
of N.N-dial kylanil ines,
by treatment
717 have been synthesized
depending
[639].
from te-
The use of lithium
of phosphorus
on the size
of 716 with
compounds
of the alkyl
R
I
CH RH’ 3
P
PC” ‘CT
‘I/--
R Ph P=iiR 3
I
CH3
Lithium diphenylphosphide chloroethenes ethylenes.
to give
depending using
and arsenide
stereospecifically upon the central
phosphinoarsinoethylenes prepared
are also
lithium
chemistry
and chlorodialkylphosphines 720 and organolithiums
mono- or diphosphino-
rivatives
and arsino[640]. %xed compounds
Other Group V and VI
have include
[641 J, sulfur
and Grignard
with 1,2-di-
atom and the stoichiometrv 718 from lithium
cyclopentadienes
compounds 719 from suliurdiimines
reagents
[642],
[643],
722 from nethylalkoxychlorosilanes
?-silylcarbanions
have been condensed
described_
the parent compound and n-butyllithium like
717
716
715
721 from
methyla!koxy(alkylthio)silanes
and lithium
from 723 and n-butyllithium
lithiosulphimide nercaptides
[645]_
of a glucopyranos- 0 have been prepared
Finally,
by reaction
of
[644],
and
sulfur-tin
de-
724 with a py-
ranose bromide [646] _ Rn=S-R
I
R’ 718
AH
W=S=NR
(CF3)2S=:lLi
720
721
‘R
719
R’ I
R”
RSeXSiRY’
CH30-Si-SPR
R3SnSLi
I
12.
724
723
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