Lithium annual survey covering the year 1974

1

LITHIUM ANNUAL SURVEY COVERING THE YEAR 1974 EDWIN M. KAISER Department 65201

of

Chemistry,

University

of

Missouri-Columbia;

Columbia,

Missouri

CONTENTS Structure

I.

and Bonding

Kinetics

II.

IV.

V.

Carbenoids

and Substitution

Reactions

X.

28

60

Reductions

IX.

Organolithiums

Heterocycles

Reagents

Lithium-Halogen

VIII.

Halogen-Substituted

36 37 56

Copper-Lithium

VII.

and Other

Metalations (Hydrogen-Lithium Exchange Reactions) At spS Carbon A. B. At sp2 and sp Carbon and at Nitrogen

Addition

VI.

11

and Mechanisms

Lithium

III.

1

Studies

and Their

Exchange

and Radical with

67

Reactions

75

Reactions

81

Reactions

84

Anions

Inorganic

and Organometallic

88

Compounds

95

References

I.

Structure Several

Stucky

tural

review

has examined

complexes studies

&Bonding

Cl].

information[2].

articles the

Langer

on chelated

Studies dealing

structure

They

metal have

have

compounds also

area of

as a probe

1973

have

Group

discussed

described

x Lithium, Annual Survey covering the year see J. Organometal . Chem., 95(1975)1-137. References p. 95

this

and bonding

and co-workers

alkali

with

the

appeared

in

1974.

I organometallic

magnetic to nature

resonance

determine of

the

strucelectrical

2

conductance

of N-chelated

polyamines coupling

[3].

structures

and aralkyl

of organometallics

both organic

and organometallic

described

Several extent

been studied

their

synthesis

performed throughout all

association

in the excited

as a function

of solvent

and their

crystal use in

Nittig

has published

his career

C6-J; the

ion pairing

in this

survey

of carbanions.

of fluorenyl

and cation

Wakefield

on their

the areas included

states

and

[4].

sections

Finally,

[5]_

encompasses virtually

shifts

organolithiums

preparations,

papers have appeared concerning

of-ionic

compounds complexed with

which includes

in solution,

a summary of some of the research chemistry

including

a book on organolithiums

and association

lithium

13 C NMRchemical the use of

Mann has reviewed

constants

has published

aryl

The

carbanions

by spectrofluorimetry

has

[7].

Two types of ion pairs, contact and separated, present in the ground state

are

also

ion

present

pairs

in the first excited state.

in the latter

example,

state

is generally

in tetrahydropyran,

separated

ion pairs

the excited

fluorenyllithium

as 70% contact

but only as separated

of protonation

(I)

is a function

turn, depends upon the solvent [83_

and solvent

separated

hydrocarbon.

(HMPA), I exists

ion pairs;

In contrast, as a loosely

the trans hydrocarbon.

selectivity

of the structured

of the loose

ion pairs

Using conductometric sulfoxide

exists

For

and 30%

ion pairs

in

state.

lo-dihydroanthracene

mostly

higher than in the ground state.

in the ground state

The stereospecificity

cis

However, the amount of separated

of g-lithium

of the nature of ion pairing Thus, in ether

protonation

associated

ion pairs

methods,

being 370 and 127 M-1. respectively

as contact

mostly the

of which gives

that the protonation directed

stereo-

while that

development.

dimsyllithium

[9].

in

of hexamethylphosphoramide

is metal-cation

by product

(DMSO) have been .found to exist

affords

ion pair protonation

It is suggested

which,

or THF, I exists

with ethanol

in the presence

is controlled

lo-g-butyl-g-methyl-g,

and dimsylsodium

partially Similarly,

as ion pairs,

in dimethyl the constants

the ion pairing

constants

3 &

&

n_-C4H9Li

\ /

sol vent

)

C2HSOH )

L?CH3

H/‘CH3 (cis --

H,>-C4H9

\ /

1:

G$0

CH3 (either

or trans.)

cis

or trans)

(I) for

lithium,

sodium, potassium , and cesium Jz_-butoxides in DMSOare 108, 106,

270, and 200 M-‘, Certain their

complexes

visible

[lo].

respectively. of fluorenyllithium

absorption

spectra

both as solids

Thus, the 1:1 complex of this

with THF exhibited than a slight the solid.

hypsochromic In contrast,

of coordination

shift

exist

probably

the spectra

exhibited

of the solid

a substantial

by variable

of lithiotrimethylstannane

as an equilibrium

M, Sn(CH3)3 The equilibria

lies

to the right

1:l

iodide

temperature

Thus, methylation

diastereoisomers

in ratios

contact

shift

atoms.

(and the corresponding

potassium

and solvent

separated

that salt)

ion pairs

[ll].

MIISn(CH313

in HMPAand to the left

obtained

in THF.

has been shown to dictate upon methylation

of II in THF and in THF-HMPAgives

of 19:l

in

presumably because

NMRstudies

W

other

ion pairs

proton

amounts of two diastereoisomers

[12].

and solution

amine nitrogen

TL-.. L--L or _z :__ __t _z__ or _r a iithiosuifoxide Ine extent ion-pair-in9 the relative

were compared

complex with pentamethyl-

bathochromic

mixture of contact

and

with TMEDAand the 1:2 complex

due to tighter

of the metal with the three

It has been determined solutions

carbanion

and isolated

and in solutions

change in the Xmax between solid

little

diethylenetriamine

were synthesized

and 9:1,

by methyl

the

respectively.

Li ~&~HW-H _.._“_..

It is suggested

References p. 95

that reactions

3

of the intimate

II

or solvated

ion pair of II are

4

stereoselective temperature

while effect

is also

In a similar

acetone

in the presence

lithiosulfide

of alkylations

the solvating

of

and of reaction

species

The results

-/ //\

pene,

triphenylmethane,

shifts

cation

repetition

diaminopolyether

[2,2,2]

gave IV and V of the experigave only IV.

studied

byNMR. Thus,the

indene,

1-phenylpropene,

and cyclononatetraene

7Li NMRspectra fluorene,

of the lithium

1,3_diphenylpro-

have been obtained

in ether,

l-l/l1

=“A LlMDn U8ls.J 111-11 CL L I-r,.

were observed.

lithium pair

Ainl*rma “‘!j ‘JWC,

species

of III with

+

were also

of cyclopentadiene,

nMc

treatment

V

salts

“I-IL-)

solvating

depends on

in terms of the type of ion pair present.

IV

)

A

OH

C,H,S ” -

Ion pairs

with acetone

In contrast,

of the macrobicyclic

are interpreted

\/

ani! not.

it has been shown that

For example,

[13].

of 25% and 75%, respectively.

ment in the presence

,“‘

III,

in THF in the absence of an additional

in yields

l-UC

of HMPAor CryptateS

noted.

study involving

the regioselectivity the presence

those

The data is explained

with respect

in terms of the location

of the

to the anion of an ion pair and the type of ion

present. Similarly,

the nmr spectra

the line

widths

of solutions

in the 6Li,

of the alkali-salts

have been reported

as a function

for

times are presented

the relaxation

to describe

the variation

7 Li,

of solvent for

and other

of biphenyl

and temperature static

in iOn pair structure

alkali

cations

of

and fluorenone Cl.51.

Expressions

and dynamic ion pair models with temperature_

It is

5

shown how, in combination with shift data, a numerical analysis of the line widths can often give detailed information about the structure of the ion pair..

Nuclear magnetic of organolithium

resonance

continued

First,

chemistry.

to be employed to study other

a method has been reported where the ‘Li

chemical

shifts

of a variety

of such compounds were determined

internal

proton

lock

of to the more usual external

instead

This method provides all

‘Li

were a function

this

Thus, the kinetics

in ether

moted by electron

(10/l

getics

positions

shifts

was

release rapid

in ether

[ 181.

temperatures, to oO.

The rate-determining

[17].

of the organolithium

and/or

on the

increased

NMR

at various

steric

time scale

In k2 = 36.0-8303T Methyllithium

in the exchanges

tetramers

which were pro-

requirement

to ascertain

and 25%, respectively

that the rate-determining and Li2CH3Br.

and is slower tetramer

ethyl -

LiAlR4 compounds

steps

(>-103sec -‘)

exhibited

distinct

in THF containing

was studied

step

This dissociation

than dissociation

deal-

in lithium-containing

of the R qroup.

at -90”.

Also

bromide

the rate

and ener-

and Li4(CH3)3Br resonances

methyl group exchange between the two tetramers

It is suggested

p. 95

due to magnetic

of methyllithium/lithium

temperatures

Though the two species

Li4(CH3)_3Br to Li,(CH,)2

References

of

by T. L. Brown and co-workers

of the exchange of methyl groups between Li,(CH3)4

tetramers’

[16].

concentration.

and the corresponding

were the 220 MHz ‘H NMRspectra

ratio)

salt

of 7Li exchange between methyllithium,

lithiomethyltrimethylsilane

exchange

in the chemical

of exchange processes

were found to be dissociation

studied

errors

relative

of standard and its

papers have been published

were determined

The

previously,

of the choice

ing with NMRinvestigations compounds.

lithium

to an

factors.

Additional

lithium,

since

new method precludes

suscepti bil ity

relative

for a general standard of comparison by which

data may be correlated

resonance Also,

the basis

aspects

at low

occurred

is dissociation

at -32’ of

obeys the equation

of the methyllithium

tetramer

7 Li and 13C in abundances of 92.6%

by heteronuclear

double resonance

experiments

6

c191with

It

was

the

dominance

Alkali alkali

shown

of

the

coupling

metal and proton

metal complexes

constants

1J(7Li-13C)

that

mechanism

hyperfine

by the

splitting

have been studied

are positive

this

is positive;

result

Fermi

is Consistent

contact

constants

interaction.

of g-dimesitylbenzene The coupling

in various solvents [20].

and are in agreement with the structure below where the

mesitY1 groups are rotated

in a conrotatory

mode.

lit-

The l3 C NMRspectra reagents

of a variety

in THF were obtained

compared to the corresponding similar

NMRspectra

1K(Sn-C) stant

are

negative

the first

the presence

formed .

mixtures

of

gave 7Li NMRspectra

the presence

spectra

methyllithium

containing

(VII)

conformers

coupling

respectively.

constants former con-

The

reduced coupling

constant

This is attributed

to

on the tin atom. with only

LiMn(C0)5 resonances

species

LiCs(CO)4 in ether

due to the pure com-

in the CO stretching

region

of C3v symmetry.

the ratio

of 2,2’-dithienyl

and

of the type Li4(CH3) nX4-n are

species

of LiMn(C0)5 in ether

of ion-paired

to 7 mole % in 13C

spin-spin

bound Group IV elements.

ESR has been employed to determine trans-trans --

Another paper described enriched

positive,

organolithium

of each carbon atom were

of a negative

Thus, no mixed tetrameric

The infrared

indicated

and

of a lone pair of electrons

Respective

[211.

reduced nuclear

observation

between any pair of directly

pounds [231.

hydrocarbons

and unsaturated

shifts

for.lithiotrimethylstannane

and PK(Sn-H)

represents

at -50°

and the chemical

The electon-mediated

in THF [22].

of saturated

of the cis-trans

ketyl

and its

(VI) and

lithium,

sodium,

7

potassium,

creasing

and cesium

[24]_

The amount of VII

of the cation

at -50”

in DME. Thus,

about 1.5 and about 4.1 for

lithium

and cesium,

ascribed

size

complexes

to steric

the binding

interaction

the ratio

between the cation

VII

in-

to VI is

The trend

and the atoms adjacent

is to

VII

powder spectra

bridged

by phenyl

spectra

can be interpreted

rings

tween the unpaired

spins

of

(VIII)

of randomly oriented

donor to a radical cycle.

metal

ketyls

bistetracyclones

obtained

dipolar

[25].

coupling

The

be-

molecules.

on lithium-nitrobenzene

that determines

anion acceptor

of

have been

in terms of electron-electron

has been Presented

thermochemical

tne alkali

at meta positions

Using ESR and NMRspectroscopy

References p. 95

with

site.

EPR triplet

a proton

of

respectively.

VI

a technique

increased

[26].

radical

anion-HMPA,

the hydrogen bonding energy of The techniqueconsistsof

a

8

The first been

two crystal

determined.

First,

structures

cyclohexyllithium-2

have a geometry of lithium There

are

six

triangular

.a-

lithium

atom contact

reported.

and B-hydrogens

atom faces

the_ orientation

It is suggested

of the cycl ohexyl

configuration

of these

have

1) was found to

which have two short

The shorter

of the cyclohexyl

derivatives

benzene (Figure

atoms in a near octahedral

(2.968(9)A,O\ distances.

and one long Li-Li

of hexameric lithium

[27]. (2.397(6)i)

is the closest

that interaction

rings with the lithium

known

between the atoms determines

rings _

Figure 2 The crystal obtained

(Figure

as a chair-form each face

2) [28].

The framework of the molecule lithium

by a bridging

lithium-lithium

Several

was calculated presence

papers were published

trimethylsilyl

and the carbanion

but also

s and p, orbitals.

a-type

which dealt structure

n-type

been

is best represented D3d symmetry with There apparently lithium

with the structures

[29].

The analysis

three-center

charge densities

of the transfer

is

atoms.

of allyl-

of allyllithium-bis(dimethy1

ether)

suggested

the

bond between the metal

bonding from the carbon s-orbitals

Negative

oxygen atoms as a result

group.

has also

only between adjacent

using the INDOapproximation

not only of a substantial

and ether

ring of approximate

interaction

The geometry-optimized

lithiums.

lithium

of hexameric trimethylsilyllithium

six-membered

occupied

significant

structure

and the

are found on the lithium

of 0.43 electrons

from the

9

ally1

n-system

atom.

and 0.39 electrons

Appropriate

bond distances

agreement with those calculated solvated

by two molecules

employed to determine is predicted

anions

the equilibrium

to have a non-planar

bridge

the effect

structure

of substituents employed included

the proton

pairs

on their methyl,

It was determined affinities

vinyl,

on the anion is an alkyl

IR, and UV spectroscopy

1,3-diheteroallyl,

substituents

Hiickel MOmodel [32].

fluoro,

tri-

of the anions with the trans-

when the only substituent

using a simple

stabilities

that electron-withdrawing

more stable

acceptor

of substituted

relative

However, the cis-anion

The x-charge distribution in allyl,

which

[30].

anion being more stable.

anions bearing

which are in

allyllithium

substituted

heteroallyl

lithium

were also

geometry of unsolvated

methoxy. and others. decrease

are listed

were performed on nine isomeric

to assess

fluoromethyl. substituents

and charge densities

to the solvated

using the CNDO/Papproximation for allyllithium

Examples of substituents

c311.

o-bonds

of ammonia [30]. CNDO/P calculations

CNDO/Pcalculations ally1

from the ally1

group.

and 1- and 3-

at C, have been calculated

INDOcalculations

on 3-butenyllithium

was found to be

and 7Li and ‘H NMR,

have indicated

a perturbation

of

the r-system of the butenyl moiety by the lithium aggregate [33]. Such a direct

observation

tions

of a similar

of a lithium-olefin interaction

Conformational directly

observed

for

interaction

ethylenation

isomers of several by proton-decoupled

tion with pmr spectroscopy,

“C

it is concluded

of these compounds is the W conformer sickle

conformer

present

in some cases.

IX

References p. 95

acylic

like

supports reactions

earlier in ether.

pentadienyllithiums

NMRspectroscopy

postula-

[34].

that the principal IX with substantial

have been In conjuncconformation amounts of the

10 ConFormationally

for

studied

comparison

Thus, treatment nearly

lithium

by lithiation

preference

(anancomeric)

with anancomeric

of X with a variety

exclusively

ence for

locked

equatorial

and deuteration for

than a simple

effect

studies

of nitrogen

delocalized

carbanions

involving

energies

lone pairs derived

a large

was further

by the CND0/2 method.

have been obtained

for

prefer-

demonstrate

XIV.

to a stereoelectronic

deserve

controlled.

the

to the CNDO/Pmethod in accounting

for

and the three

mention.

of n-delocalized [37]. isomeric

is not the case for

the lithium

ab initio pyrazine

and cr-

For example, picolines

the same trend as the negative

Second,

The

rather

First,

from 14 azabenzenes

this

or

XIV

on the stability

of toluene

of hydrogen exchange rates;

tions

(>6kcal/mole)

1351.

exclusively

thermodynamically

calculations

by the former method follow

calculated

affords

XIII

the effect

lated

derivatives

That there exists

is ascribed

and is largely

NOD0method has been found superior

deprotonization

have been

by DC1 of XII and XIII to mostly afford

XII Two other

(XI).

position

such stereoselectivity steric

cyclohexyllithium

of electrophiles

products

in the equatorial

2-lithio-1,3-dithianes

ion pair

energies

orbital

[37].

calcu-

logarithms

deprotonization molecular

the

calcula-

The lowest

11

energy conformation of

the

pyrazine

consists

ring

The enthalpy

of the lithium

along

the

differences

C2 aXiS passing

[38].

For example,

ether were -54.5+0.2

and -62.8

numbers were realized determining

relative

provides

the first

quantitative

bearing

non-bonding

electrons

developed

to study the effects

trimethylsilane the above species II.

Kinetics

proximate direct

the migration

proceand

by a substituent bond.

method has also

been employed

on the heats of interaction

solvated

of

and lithiomethyl-

that base coordination

the rearrangements

aluminum hydride

Many interesting stemming

from

relative

and actual

using lithium

to hexamers of

te_tramers.

rates

with significantly

have appeared in the last

reactions

in cyclohexylamine [42].

by organolithiums.

enhanced s-character.

Thus, the

and found to be 1.20 and values

for

set -1 , respectively.

than the reported

hybridization

year

cubane were determined

The corresponding

were 1.0 and 5.53?0.05

cubane is 1,000 times more acidic to the altered

section

rearrange-

[41].

of exchange of deuterated

, respectively

compounds where

and Chen has reviewed molecular

or metalation

cyclohexylamide

under the same conditions

of organosilicon

reductions

papers in this

ionization

6.781-O-48 set-’

p_ 95

to

terminus is oxygen [40]

ments in lithium

References

about stabilization

bases with &-butyllithium

directly

negative

and Mechanisms

Brook has reviewed

is ascribed

organometallics

in

in the

a straight-forward

to the carbon-lithium

interactions

The data suggest

may lead

to ethanol

for

calorimetric

tetrahydrofuran

[39].

in di-c-butyl

solutions

of isomeric

information

plane

atoms.

the 9- and p-isomers kcal/mole,‘respectively; slightly less

enthalpies

of steric

THF and substituted

by adding their

the values

in the

through the nitrogen

in TMEDA. The method provides

dure for

A previously

a position

between g- and p-lithioanisoles -

ether and TMEDAhave been determined a calorimeter

occupying

value for

at the anionic

benzene That

cyclopropane

carbon atom to an orbital

12 Lithium cyclohexylamide equilibrium lo-phenyl amine,

acidities

[43].

pka of both

ene whose pka = 18.49). to contribute

&

After

correction

The completely

Lewis

aromatic

employed to obtain (XV)

adduct

formation

(relative

canonical

&

-

with

(

)

I

4

V

to 9-phenylfluor-

&

‘\

-1

:’

’

‘I QI

I

I R = H or C5H5

XVI

XV’ In contrast 14

C labeled

to an earlier

ethyllithium

in the reaction mediate.

[44].

Steric

The results

requirement

c--butyllithium

z-butyllithium.TMEDA

aromatics

metalation

in

in hydrocarbons.

of 3,5_diethylanisole

by

that adduct XVIII is not an intermediate also

eliminated

were studied

XIX as an inter-

on various

3-alkyl

with n- and t-butyllithium

have been correlated

of the organolithium

Z- t-butyllithium.

XVII

CIDNP results

in metalations

and other

TMEDAcompiexes. steric

demonstrated Negative

factors

3,5-dialkylanisoles

proposal,

is related

hydrocarbons

the

form XVII is thought

\ /

the

and its

hybrid.

I V

for

compounds was found to be 15.8

to the resonance

I)

was also

of 9-mesityl-9,10-dihydro-9-boraanthracene

derivative

the

in cyclohexylamine

and their

with the concept to the oligomer

> n-butyllithium

and

that the size

where

in ether

>

13 It has been found that

tetraenyl

the stable

ten r-electron

bicyclo[4.3-l]deca-

anion XX can be prepared at low temperature

by fi-butyllithium

Treatment of XX with bis(dimethylamino)ethoxycarbonium though,

gave the closed

nonafulvene

norcaradiene

XXI rather

[45].

tetrafluoroborate,

than the desired

bridged

XXII.

z-C4HgLi TMEDA ’ 0” +

2COC2H5BF4 vs

\

\

q

XXI

Treatment of the’dibenzannelated g-butyllithium red solution contrasted 3,4:5,6

in cyclohexane

isomer

ionization

(XXIV).

aromatic

reported

The authors

because of its

the benzene .rings.

References p. 95

at -20” was found to instantaneously

of the non-benzenoid with the previously

1,2:5,6-dibenzocyclononatetraene

biphenyl

anion XXIII [46].

rather

conclude backbone,

slow related

give a

This is to be conversion

that XXIV undergoes not because

with

of the

such slow

of the annelation

of

14

It has been determined thermally

labile

isomerization trans-isomer

[47].

that the related

Thus, at 56” in ammonia, XXV undergoes

The isomerization

the parent cyclononatetraenyl The reaction

unidirectional

x 10-5sec -1 , aGt- - 26.2 kcal/mole]

[k=(2.56+0.22) XXVI.

monobenzo system (XXV) is

is surprising

anion prefers

of XXVto XXVI is rationalized

in light

to isomerize

give

the

of the fact

that

to

from -trans

in terms of diminution

to -cis.

of peri

H-H

interactions.

XXVI

xxv Attempts were made to prepare dianion nitrile

with E-butyl-

subsequent

reaction

bromide afforded

and methyllithium of the carbanion

bis-products

, e.g.,

XXVIII, NMRindicated

to give XXIX had occurred.

sequential

metalation

-4z&N

..A

at low temperature

[48].

with chlorotrimethylsilane

metalation

z

XXVII by metalation

Thus, products

like

of 3-buteneThough or benzyl

that only monoXXVIII arose via

and alkylation-

(CH313Si Li+

ZLi+ XXVIII

XXVII Several with them. lithio

salts

other

papers dealt

Thus, four different

with cyclic

XXIX carbonitri

cyclopropanenitriles

by strongbasesinTHFat-78°

les or compounds isomeric were converted

[493. Though the carbanions

to their were stable

15 at this

temperature,

apparently

by conrotatory

by the conversion process.

three of the salts orbital

underwent thermal opening at ~-25”

syrrnetry control_

of XXX to XXXI, a reaction

The latter

reaction

opening of a cyclopropyl

represents

also

the first

anion to an ally1

The process is illustrated

effected

by a photochemical

example of a photochemical

anion.

CN

LiNC THF -

) /

-78”

H5C6

"&6 to -25”

xxx i CN

C,H,-A

C6H5

c

H20 Li+

Alkylation

of lithionitrile

XXX11 and related

of hydrogen bromide to 1-chloro-4-phenylcyclohexane trate

the recently

described

and methylenecyclohexanes ial

and axial

selectivities

are attacked

are ascribed

to different

the trigonal

atom with the symmetric B-carbon-carbon

xxx11

P_ 95

atom from the equitor[SO].

on the two faces of the p-orbital

bonds.

CN

RX > -3--f

densities

atom due to the interaction

/NLi

References

double bonds of cyclohexanones

at the ring trigonal

electron

as addition

are used as examples to illus-

sides by electrophiies and nucleophiles, respectively

plane containing trigonal

rule that exocyclic

compounds as well

Such

of the of that

16

In contrast taining

its

to lithiocyanocyclopropane

configuration

cyclopropane

in aprotic

XXXIV retains

its

-52O L-511. The data suggests an

adjacent

negative

in benzene

to

give

presumably proceeds for

one

example

configuration

of strong

cis-trans --

sulfones

isomerization

via intramolecular

follows.

occurs

lithioisocyano-

of

group.

Stabilization

the

ring

proton transfer.

fusion

of such

effect.

and sulfoxides

were treated

to

able to delocalize

via an inductive

bases with sulfones

bicyclic

of main-

to a high degree in THF at -72”

that the cyano group is better

group probably

Three G-fused

be studied.

the corresponding

solvents,

charge than is the isocyano

a charge by the latter

The interaction

XXX111 which is incapable

continues

to

with n_-butyllithium [52].

A portion

The

process

of the proces!

17

Reaction t-butyllithium

of various

has been studied

carbon-sulfur

versus

sulfoxides

RSOCH2Rl

+

with methyllithium,

to.determine

bond cleavage;

R,Li

the relative

the latter

Li RSOCHR,

+

vs

process

diisopropylamide ration

at sulfur.

Such inversion

are thought to be SN2-like (e.g.,

reactions

processes

rather

and

of o-ionization

a new sulfoxide

t531.

R,SOCH,R,

XXXVI

is best effected

and that the cleavage

extent

affords

RSOR, or

xxxv

It was found that a-ionization

n-butyllithium.

by methyllithium

occur with inversion

are extremely

than involving

or lithium

facile

a hypervalent

of configu-

even at -78” sulfur

and

intermediate

a sulfurane). Other workers,

in similar excess

though,

[541.

with -p-tolyl

Similarly,

XXXVIII with organolithiums to olefin

the presence

Thus, sulfurane

reactions.

-p-tolylithium

products

suggest

and lifhium

XXXVII is proposed

sulfoxide

it is suggested involve

alkylsulfinate

of such hypervalent

to qfford

intermediates

in the reaction

-p-tolyl

that reaction

intermediates

sulfide

of

and other

of episulfones

like

such as XXXIX which decompose

[55].

OLi

XXXVI I

,Referencesp.95

XXXVIII

XXXIX

18

Many papers describing variety

of monoolefins,

n-butyllithium new anionic

of ally1

and unconjugated

anions appeared in 1974.

dienes

in TMEDAto study allylic

di-

were treated

that aromatic

to form highly

lithiated

in TMEDA,the Z-isomer (XLI) by a ratio

gave 46% Z-P-octene,

(XL) of this

8% E-2-octene,

n_-butyllithium possible

)

ionic

period species

Alkylation

Z-E-butene,

or E-2-

of only 15 min [57]. predominates

of this

At 35O

over the E-isomer

mixture with n-butyl

bromide

and 46% 3-methyl-1-heptene.

XL1

also

to afford

beenprepared

a 3:2 trans:cis

mechanism of the isomerization

XL and XL1 is discussed.

is not

(_J&+J-’

-2

XL

Crotyllithiumhas

by NMRand by alkylation

prepared from l-butene,

using a reaction

of about 85:15.

That the

systems.

has been readily

butene and t-butyllithium

[56].

or homoaromatic stabilization

---__ &c ‘\ ; I .-__’ (W

Crotyllithium

A

with excess

and trimetalation

compounds shown were formed was established

The work demonstrates necessary

chemistry

from either

Z or E-XL11 and methyl-

mixture of the organometallic

1581.

between Z- and E-crotyltrimethyltin

or A via

~

19

CH$H=CHCH2Sn(CH3)3 XL11 (Z or E) A paper appeared that describes to 1,3-dienes

in the presence

to the initial

cycloadditionsofpentadienyllithiums

of furan or toluene

absence of added 1,3-pentadiene XLIV, and other

stepwise

159-J.

For example,

The furan and toluene

products.

pentadienyllithiums

both in the presence

as well

1,4-pentadiene

and in the

affords

XLIII,

presumably act as proton

as to 1:l

donors

adducts of the latter

with

1,4_pentadiene.

n-C4H9Li THF

-

)

Li+

II + CH3CH=CHI 4 Q CR3

cH3

CH=CHCH3

XL111

Ally7 action

anion XLV was observed

to afford

corresponding

0-benzyl

ether

XLVIII [61,62].

governed by electronic and perfluoroacetone References p. 95

to undergo an intramolecular

cyclization

XLVI and XLVII in a ratio of 3:7 in 55% yield

Two papers described lithium

XLIV

behaved similarly.

the ambident nucleophilicity Reactions

effects give

A two-step

compound; for

XLIX and L in high yields,

The

mechanism is proposed.

of gem-dichloroallyl-

of XLVIII with aldehydes

of the carbonyl

[60].

re-

and ketones example,

respectively

[62].

are

acetone The

authors

speculate

that such selectivities

HSABapproach.

XLVIII also

gives

might be explained

products

methyl iodide,and

water,

types of products

with chlorotrimethylgermane

products

7

of LI (M=Li)withallyl

a-products.

&co2c2HS

LI

YH

TH

CF3;-CH2CH=CC1

Interestingly,

CF3

of dienolate

ally1

halides

LI was studied [62].

bromide gave mostly the expected

y-products

from SN2- rather

afforded

ally1

a-product

halides

LII,

from the copper enolate

(LI,

as evidenced

$cHco2c2HS

LIII

LIII

led to

studies.

LII

as a

Though alkyla-

LIT and the y-product

than SN2 substitutions

Fco2c2HS

2

L

and various

halide

and both

[61]_

of 44~56. . The use of more complicated

appear to arise deuteration

L with bromotrimethylstannane,

in the alkylation

of LI (M=Cu) with this

in a ratio

XLIX with chlorotrimethylsilane

CH3

of the metal cation

reaction

using Pearson’s

XLIX

The regioselectivity

tion

like

$H3

2

XLVIII

function

like

CH2=CHCCl

CH
XLVII

XLVI

XLV

M=Cu) from

21 Aldol-type investigated

condensations

with a variety

to be more nucleophilic arising

from attack

of ally1

anion

of aldehydes

( C6H6)2

_

and ketones

at Cl towards alkyl

at C3 were obtained

LIV and related

Though LIV appears

only alcohols

halides,

in this

[64].

compounds were

(C6H5)2~=~~~~~6H5

CHC6HS

’

I RR’ COH LV

LIV

to give

indenyllithium

1-alkylindenes

lithiums

gave mixtures

LV

study.

Lit

Similarly,

iike

underwent alkylations

in good yields

[65].

with various

Though alkylations

of LVI and LVII, methylation

alkyl

halides

of methylindenyl-

of certain

alkylindenyllithiums

gave LVIII in good yields.

A variety

of workers continued

bases _ Thus, detailed a-lithiobenzyl the authors could

region

References

ethers to suggest

be trapped;

isolated;

LVIII

LVII

LVI

has been described

[66]_

arising

shifts

The following

the mechanism shown with LIX:

and 3) the NMRsignals

p. 95

rearrangements

study of the mechanism of 1,2-aryl

2) no products

during the first

to investigate

1) no aldehydic

from LIX were obliterated

by

of several

observations

from aryne intermediates

minute of reaction.

effected

led

products

could

be

in the 4.0-8.0

ppm

22 Li+ C6H5O-CHC6H5 +

C6H5-

Li+ !C6H5-H-C6H5

-

LIX

A new, stereospecific reported

to give

For example,

the

the

of

geometry

oxide also

lithio

migration

vinyl

to

group;

the

involve

LX1 was also

lithio

carbanion

fragmentation

to

other did

hand, not

vinyl

though

vinyllithiums

with

of

deuterium

ethers

benzyl

rearrange.

[67].

preservation

trapped

ally1

has been

yields

LX11 with

Some but not all On the

rearrangement

in excellent

SaltofetherLXrearrangedto

rearrangement.

metalation,

thought give

the

in the Wittig

and benzylvinylcarbinols

and chlorotrimethylsilane.

underwent

to

divinyl-

the migrating

underwent

are

vinyl

studied

vinyl

sulfid

The rearrangement

and carbonyls

which

recomb

products. OH Li

n-C4HgLi TMEDA )

‘gH5 -,

c6H5-h

b

LX1

(e-g.,

sulfides

LXIII)

methylation,

which 6,

with

lithium

undergo

LX11

diisopropylamide

a [2,3]

sigmatropic

dithioacetals

y-unsaturated

I

C6H5e

I

LX

Allylic

1

%

were found rearrangement

(e.g.,

to give

carbanions

to afford,

after

LXIV) [68].

CH31

LX111

LXIV

MIND0/3 calculations ment indicate

the

reaction

for

a Pericyclic

could

occur

mechanism

by a concerted

for

the

pericyclic

Steven’s path

rearrange[6g].

23 Though the calculations

do not allow-a

distinction

between the above and a

radical pair mechanism, they do suggest that the G!oodward-Hoffmann rules break down for

very exothermic

Base promoted reactions LXV-LXVII elimination

give

arising

mono- and diquaternary

from the Steven’s

LXIX), pr displacement

(e.g.,

ence of the quaternary leading

reactions. of bicyclic

to give products

nitrogen

to LXVIII was also

may

observed

rearrangement Ce.g.,LXVIII),

are controlled

atom [70].

ammoniumsalts

by the acidifying

The novel vinyl

Steven’s

on benzylvinyldimethylammonium

influ-

rearrangement hydroxide

to

LXX in low yield.

+ -Q

+n+

C6H5CH2-+-l_,N~H2C6H5

‘6”gCH2

‘sHgCH2

ci

u

ci

LXV

ci

ci LXVII

LXVI

CH=CH2 E ““’

LXVIII

LXIX

Two papers described salts salt

Hb(CH3)2

with alkali

the differences

LXX

in reaction

of quaternary

amides in ammonia versus n_-butyllithium

ammonium

in pentane.

First,

LXX1 with either potassium amide or lithium amide gave -cis:trans-cyclo-

octene in a ratio of 32:68 [71]. Most of the deuterium had been completely exchanged prior

to elimination.

cis:trans-cyclooctene

in a ratio

deuterium was realized versibly salt

with alkali

before

References p_ 95

of 70:30;

elimination.

amides and irreversibly

LXX11 with lithium

dimethylbutylamine.

In contrast,

LXX1 with E-butyllithium less

than a statistical

Thus, the N-ylide

The latter

contained

loss

of

is formed re-

with n_-butyllithium.

amide in ammonia gave undeuterated

gave

Second,

norbornene

and

6.7% deuterium and the reaction

24

proceeded

by a z-elimination

same products

except

This

[72].

the amine contained

by the syn-a’&mechanism

salt

with

E-butyllithium

99% deuterium;

this

gave the

reaction

proceeded

shown (LXXIII).

CH3 1, 1?4Hg 3

0

I-

LXX1

LXX11

Though the effected ether

sulfonamide-aminosulfone

by sulfuric

or THF [73].

acid, Thus,

it

20°

pared

example reaction

rearranged from stannane

several

has long been known to be

been effected

LXXIV has been converted

by organolithiums

to LXXV, apparently

LXXV

Another

at

rearrangement

has now also

LXXIV

the Wittig

LXX111

other

C6H5CH2NCH2Li

of the of ethers

to lithio

rare

rearrangement

LXXVIII

of tertiary

LXXVI.

in at

LXXIX and E-butyllithium,

[74].

least

amines analogous Thus,

83% yield.

a process

carbanion LXXVII

was pre-

a-l ithiomethylamines. C6H5CH2CH2rLi CH3

CH3

C6H5CH2yH2Sn(n-C4Hg)3

LXXVIII

CH3 LXXIX

to

LXXVII

used to synthesize

I

LXXVII

via

LXXVI

has been discovered salt

in

25 A new rearrangement has been reported gave a transient

[75].

of dialkylmethyl(Z-triphenylsilyethyl)arnnonium Thus, treatment

red colored The reaction

fourth

of quaternary

reaction

the Steven’s,

of LXXXwith ri-butyllithium

mixture which,

in good yield.

upon work-up,

which presumably involves ammoniumsalts

the Sommelet-Hauser,

gave silylamine

with strong

bases and stands

(C6H5)3S&

LXXX1 descriptions in 1974.

germanes where silicon

of rearrangements Wittig-type

of base. version

involving

rearrangements

and germanium are the migrating

which proceeds

Pr/:(CH3)2 CH2:CH2

cc-silylcarbinols

alkoxysilanes

Alkoxysilane

LXXXVundergoes

stereospecific

at the benzyl

carbon atom [77].

and germanium and

atoms have been discussed to LXXXIV [76].

This

of LXXX111 and LXXXIV is

which involves

to neutral

silicon

of alkoxysilanes

convented

because of equilibration

contrasted with the Brook rearrangement

of neutral

beside

LXXX11

in a full paper; for example, LXXXIII is rapidly rearrangement

a

and the Hofmann reactions.

(C6H5)3SiCH2N(CH3)2

LXXX

also were published

LXXX1

LXXX11 represents

I-

other

below -15O

CH

f (C6H5)3SiCH,CH2N(CH3)3

Several

ylides

the reverse effected

conversion

by catalytic

rearrangement

The reaction exhibits

amounts

with 99% in-

k "/k,, = 2454, the

highest value reported for a metalation reaction.

/ ‘sH5’<

C,H,&OSi(CH3)3

3

H5C6%_ 9+-Osi

OLi

examples of similar

germanium from sulfur LXXXVI is converted

l,P-anionic

to carbon have also

rearrangements

been described

to LXXXVII by stoichiometric

CW.

of silicon

p. 9s

and

For example ,

amounts of strong

bases.

The reverse conversion of LXXXVIII to LXXXVI is effected by a radical References

(C”3)3

LXXXV

LXXXIV

LXXX111

The first

Si (CH3)

initiator.

-26 ,Si(CH3) 3 C6H5CH

,Si(CH ) 33 "6RSC: SLi

C5H5CH2SSi(CH3)3

\sH LXXXVIII

LXXXVII

LXXXVI

Finally, aminomethylsilanes like LXXXIX have been rearranged to methylaminosilanes like XC in high yields by catalytic amounts of r-&butyllithium1791. A mechanism is proposed.

(CH3j3Si CH2C6H5 ! H3 xc

LXXXIX

A'few miscellaneous papers deserve mention

In contrast to the well-known

directed ortho-metalations of amines like XCI, metal-halogen exchange of XC11 by g-butyllithium at low temperatures followed by addition of water gives XC111 and XCIV[80]. Since no productfromanc-lithio derivative is observed, coordination of the metal cation with the amine nitrogen atom seems unimportant.

N(CH3$

Cl

N(CH3)2

c xc1

xc11

xc111

XCIV

A remarkable solvent effect has been found'in the interaction of aryl bromides with primary aliphatic organolithiums [Sl]. Thus, such reactions in ether give metal-halogen exchange to afford aryllithium reagents. Similar reactions in THF though give Wurtz-Fittig products (ArR) in yields of 52-87%.

The latter reactions are thought.to occur

by SN2-like

via metal-halogen

exchange -followed

by alkyllithiumr,

the lithium

reactions.

The cyclization

of 4,6-dihalononanes

anions of naphthalene has been studied

and biphenyl,

[82,83].

and lithium

The cyclizations

amalgam to afford

normally

occur

manner indicating that the halogens are cleaved in a

less

thermodynamically

in most cases. intermediate

stable

cyclopropanes

in a stereoconvergent

non-concerted mode.

&-l,Z-di-n-propylcyclopane

It is thought that “s-cyclopropane”

radical

The

is formed predominately does not participate

as an

in these reactions.

Second order

rate constants

for

the exchange of phenyl radicals

phenyll i thium and l4 C-labeled

bromobenzene were found to increase

ing solvent

< ether c dioxane c THF [84].

order:

between the enthalpy

phenetole

and the entropy

of phenyllithium

between

in the follow-

A linear

solvation

correlation

in these

solvents

was found. The interaction

of 1,6_dihalohexanes

radical anion have been shown to give

significant

in similar

are important

in contrast, that at least

reactions

since

cyclohexane

or sodium naphthalene

hexane, cyclohexane,

amounts of C12-hydrocarbons.[85].

not significant cations

with lithium

of 1,4-

cyclohexene,

The latter

type of compounds are

and 1,5-dihaloalkanes.

hexane is the dominate reaction

and I-hexene

predominate

part of the hexane arises

when

via radical

and

Metal 1i c

product

when M=Li;

M=Na. It is suggested

anion XCV.

. -

I=+

+n_-C6H14

mzM+ +C1(CH2)6C1 -( 6 M=Na

Another paper presented action References

of benzyl p_ 95

evidence

and benzhydryl

halides

that nearly

n_C4HgCH=CH2

,

all

dimer formed from the re-

with naphthalene

radical

anions

(M=Li.K)

28 involves

precursor

a carbanion

established

trap,

The reactions

t-butyl

or t-butyl

radical

alcohol-G-d

of XCVII

naphthalene

have

to XCVIII

radical

Since

the authors radical

by Garst [86].

anion followed

is

1.70

with

lithium

E-butyllithium,

by quenching with deuterium oxide

been found to give XCVII and XCVIII

the anti-lithium

pre-equilibrium

and absence of

compounds XCVI with lithium,

anion (X=Cl).

conclude

This was

alcohol.

of the anti-halo

and lithium,naphthalene

(X=Br).

suggested

by comparing the amounts of dimers in the presence

the carbanion

ratio

as previously

(X=Cl)

and

The

[87].

>lOO:l with lithium

Only XCVIII is formed with n-butyllithium reagent

once formed is configurationally

that the stereoselectivity where the anti-radical

is governed Primarily is less

stable

stable, by a

than the syn-

radical _

d2bc

d zi!A L.

H

D

X

XCVII

XCVI

XCVIII

(X=Cl, Br)

Despite

previous

cene by methyllithium products

electron

can be effected

are formed including

methyllithium

to anthracene

transfer-alkyl

it has been found that alkylation

reports,

XCIX

gives

transfer

photochemically

and C.

[88].

In ccntrast,

mostly XCIX. versus direct

Possible addition

of anthra-

A variety

thermal addition

of of

mechanisms including of methyl carbanion

are discussed. H3

053 000

XCIX

@-@JCH3 C

29

Finally, di-t-butyl lithium

three

peroxide.

Ethyllithium

t-butoxide,

The product

t-butoxy

ethyl

rates

cross-combination

of these

related

and butane [89].

to the known values

iz-butyl

ether

reactions

have been found to accelerate

the reaction

of E-butyllithium

in heptane [90]_

The accelerating

effect

> (p_-C H ) 0 > (i-C H ) 0 > phenetole. 492 372 by various

lithium

Lithium Carbenoids The first

ion other

description

alkoxides

CIII and.not

above

in

addi-

with this

in the order THF

reaction

is

not

the

Organolithiums

trapping

has been reported

chloride

from

[91]_

of the successful

Experiments are presented

CII.

The

and Other Halogen-Substituted --

than by protonation

CI with lithium

Electron-donor

decreased

for

of the

is thought to arise

cage.

affected

like

ethylene.

in a solvent

> ether

ester

ethane,

and disproportionation

The ethyl

with

peroxide: has been found to afford

can be quantitatively

radicals.

of organolithiums

radicals

peroxide

III.

ether,

of the combination

and ethyl

the reaction

with this

t-butyl

distribution

the relative

tives

papers have described

presence

to suggest

of a halodifluoromethide

[92]. of

Thus, treatment

various

ketones

gave

products

likeCI1

arise

of species from

from difluorocarbene. OH I CF3CCF2Cl

Cl F2CC02CH3

LiCF$l

t 6H5 CI

An improved

from alkenes volves lithium

in yields

or potassium

p. 95

for

CIII

the preparation

of gem-dichlorocyclopropanes

of 75-968 has been described

mixing chloroform,

A variety

Rekmxs

procedure

CII

salts

the alkene, of

of novel ring

[93]_

and a sterically

The procedure

bulky base like

triethylcarbinol. systems have been prepared

using

carbenoid

inthe

30 reagents.

The first

example of a bicyclo[ki_l_O]octadiene

was prepared

mOnOOlefin)

at -60a [94]. methyllithium

0

at -48”

to -50”

_ii

‘r! \

’

Ii

,,’

i-_

P

CVI

product

that would arise

On the other the quantitative carbon

mostly CIX arising

insertion

into

from this

route,

hand, reactions preference

hydrogen bond [97].

ethylenediamine

CVIII with methyllithium

into a primary carbon-hydrogen involve

from CVTI and

r’

and 36” has been found to afford

usually

derived

)... I

!I

of dibromocyclopropane

the cyclopropylidene

CV with n_-butyllithium

6

d-c1

cv

The reaction

reactions

chloride

[95].

v

CIV

loo,

of vinyl

Ring CVI was prepared from a carbenoid

r

\

by reaction

CIV (and its

for

tertiary

bond [96].

derived

into a secondary

sion of CXIV to CXV and related

Similar

bonds,

the

study.

from CXI substantiated rather

than a primary

reduced by lithium/

compounds were obtained

compounds [98].

of

-Though such

carbon-hydrogen

Product CXII was subsequently

to give CXIII.

from insertion

CX, was not found in this

of the carbenoid insertion

at -40°,

in the conver-

CXII

CXI

CXIII

CH \3

Br Br .OCH3 Z

6

H3Cb

a CXIV

cxv

The action cyclopentenes

of n-butyllithium

on vinyl

chlorides

CXVIII and CXIX in good yields,

CXVII

Two papers have described

the mixtures

p. 95

gives

a new method of converting

via oxaspiropentanes

below where the carbenoids

[99]_

/!!ylr”

CXVI

to cyclobutanones

CXVI and CXVII lead to

respectively

-~‘uC’

References

OCH3 ,\>’

[lOO,lOl].

are prepared and ketones

CXX which can be isolated

dibromocyclopropanes

The process

is illustrated

added at < -90”;

in some cases with basic

warming work-up

32 [loo] or isomerized to cyclobutanones with either acid or silicon dioxide.

wide variety

of specific

A

examples are listed.

I:

ri-C4HgLi \ THF ’

R5CR6I\

8’ \

/R6 COLi I

cold

R4

R2

acid

‘R3

cxx A practical

synthesis

has been described

The procedure

[102].

the carbenoid

reagent

of preformed

carbenes.

studied

of polyhalomethyllithium

in the presence

represents

a highly

like

like

preparation

and avoids

method of effecting

of

Carbenoid precursors

A separate [103].

CXXI

the problems

(X=Cl, Br, and I) and CHX3 (X=Cl and Br);

CXXI to ketones

effective

adducts

the -in situ

An example is shown below.

have included.CH2X2

of adducts

involves

of the carbonyl

the adducts were formed in > 86% yield. version

carbonyl

paper described

The overall

process

ring enlargements

most of

the conthus of one

carbon atom.

CXXI

Carbenoids ketones _

have been reacted with electrophiles other

Thus, reaction

of lithiodichloro-

than

aldehydes

or dibromomethane with esters

and

gives

33 a,a-dihaloketones followed

like

by treatment

CXXII in good to excellent with diazomethane

formamide of cyclopropyl

derivative

yields

and reaction

[104].

Carbonation

with N-methyl-N-phenyl-

CXXIII give CXXIV and CXXV, respectively

[1053.

P

(CH3)2CHtCHBr2

lated

alpha to oxazines

to eventually

example,

afford

benzylation

of

CXXVIII or CXXIX depending use

of

optically

a-methoxy-

and

active a-chloro

and oxazolines

a-chloroaldehydes

CXXVI

affords

on the

oxazolines acids,

cxxv

CXXIV

CXXIII

CXXII Carbenoids

-H

02CH3

CXXVII

choice

have been prepared,

or a-chloroacids which

respectively

cl071

[106,107].

can be converted

of subsequent

CXXX and CXXXI

then alky-

afford

reagents optically

to

For either

[106].

The

active

-

Li CXXVII

CXXVI

R

Cl CH2.

HOCi;CH2C6H5

cxxx

CXXIX The preparation has been described

References p_ 95

CXXXI

of new 1,3-dimetallacyclobutanes [lOS].

For example,

treatment

using carbenoid

CXXXII

of CXXXII with dichlorodi-

34

methylsilane

gives

CXXXIII in

and a mechanism for

p3)3Sq

their

a yield

formation

of

36%.

Other

examples

are

mentioned

is postulated.

2 CBrLi =.S+iiZ

CXXXII

&#ethyl in fair

substituted

to gbod yields

cxxxv [109]_

CXXXIII

Several

a,#&unsaturated

ketones

by a new one-carbon specific

homologation

examples are listed

to 25O

2 CH3Li THF -95”

(CXXXIV) may now be prepared

)

>

involving

in the paper.

2N H2S04

Q\W

.\

k1

k2

CXXXIV

cxxxv A new synthesis described

cyclopropane

[llO].

of alkenylacetylenes

from a,@unsaturated

The method is illustrated

by the conversion

H

n-CqHqLi THF

‘sH ’

-70° CH3 cxxxv I

to 25O

‘gH

H

ketones

has been

of CXXXVI to

35 Vinylsilanes action

may now be prepared by a new synthesis

of organolithiums

The reactions

involving

with a-chlorovinyltrimethylsilane

presumably proceed

the inter-

(CXXXVIII) [ill].

via CXXXIX as illustrated

in the preparation

of CXL.

t-C4HgLi pentane ’ cold

(CH3)3SiF=CH2 Cl

CXXXIX

cxxxv111

CXL

Halogenated ynamines have been synthesized For example,

[112].

‘I\

CXLI is converted

,N(C6H5)2

from polychlorinated

to CXLII in low yield.

n-C4HgLi

C1C=CN(C6H5),

THF-ether) cold

/c=c\ Cl Cl

enamines

CXLI

Finally,

two other

methyllithium carbenoids

papers deserve

Other reactions

CXLIV [113].

Protonation

of CXLIV including

to afford

carbenes

hydroxylamine

derivatives

via nitrenoid

CXLVI [114].

Referencesp.95

brief

mention.

have been added to dialkylthioketenes

like

thermolysis

CXLII

offers

First, like

of CXLIV gives

trapping

are discussed.

with certain Second,

phenyl-

and

CXLIII to afford thioethers

(CXLV).

electrophiles a-deoxysilylation

a new method of generating

nitrenes

and of perhaps

36

L

o=

L

RLi ether -78O

c=s

1.

SR

CH30H

-C’

o-

1‘

CXLIII

“zO

Yi

CXLV

CXLIV

1. 2n_-C4ti9Li

loo0 )

C6H5NHoH2. 2Cl Si (CH 3)3

‘6”S!

CXLVI

Metalations

IV.

Several

(Hydrogen-Lithium

reviews

have been concerned

Thus, the mechanistic their

effect

summari-zed al

kyl benzenes,

The

ethers,

diamine complexes of

elastomers

similar cussed

portions

[120].

dealing

aspects

sulfides,

and other

carbanions

aromatics,

reagents

[122].

cyclopropylides

via

amines with respect

metalations

to

have been

of

Metalation

[118],

aromatics,

by organolithiums

and polymetalation

and arylacetylenes

of a variety

of this

compounds.

compounds by n_-butyllithium-tertiary

A review of the chemistry

information

The use of carbanions

the

[116,117].

with the preparation

contains

of

of organic

of organolithiums

initiators

metalations

with interaction

A paper concerned

from

synthetic

by anionic

Directed

[119].

tertiary

and properties

have been described

prepared

with metalations

of chelating

reagents. of acetylenes,

been reviewed

of basic

aspects

on the reactivity Cl IS]_

Exchange Reactions)

have been dis-

of substituted

aromatics

of carbon suboxide

on the synthesis

with organic of the latter

have

contains

compound with organolithiums

of olefins

by

[12l].

phosphonate using a variety

The types of compounds that can be prepared to date cyclqpropanation

of allylic

and

sulfoxides

regioselective alkylations has been discussed

epoxides

have been sutnnarized [123]

to prepare allylic [124].

alcohols,

1,3-Anionic

and in

cycloadditions

37 of organolithiums allylic

L-1251 and recent

organometallics

chemistry

including

of a-metalated

advances in the chemistry organolithiums

isocyanides

[127]

compounds via intramolecular

alkylations

the determination

of acidity

constants

oxime derivatives

[130]

A._ At d Several

[128].

and 0-organometal

Spiro Finally,

hydroxylamine

as synthons of various

mercaptan has been converted

successively

Though E2 has usually

with two different

ketones,

been methyl iodide, and others.

CXLVII

to its

salt

El and E2 to

of 67:30 to 80:20

[131].

halides,

TMEDA ) THF-hexane

epoxides,

Treatment of CXLVIII and CXLIX with methyl

SE2

CXLVIII

c-C4H9Li

CXLVII

CXLVII

CXLIX

1. n-C6H13X \ 2. CH31 ’

CXLVIII iCXLIX

I

CH3SH HCl gas 3 min.

NBS, AgN03 ’ CH3CN/H20

References

p. 95

and

functional

dilithio

electrophiles

E, can be alkyl

E-i

“CaH’3Vjs

The

have been reviewed.

give a mixture of CXLVIII and CXLIX in a ratio

//-YfH

of carbocyclic

have been discussed

papers have used carbanions

which is treated

aldehydes.

have been described.

and synthesis

[129]

of

_Carbon

Thus, ally1

groups.

[126]

of a variety

3 min.

c-C6Hl 3\/\ / CH3S

SCH3

38 mercaptan

followed

in yields

of

by hydrolysis

65-962.

with

NBS and silver

nitrate

gives

aldehydes

The entire procedure is illustrated for the preparation

of nonanal. Related

metalated

[132,133,1343.

ethers

Such carbanions

predominately a function

allylic

y to oxygen of

react

to afford

R, more y-product

CL serve with

alkyl

(CLI)

being

confirmed

of y:a

ratios

E-hexyl of

these

of CL (R=Si(C2H5j3) gives

iodide species

is

has been independently

CLI:CLII)

have been found

by alkylation of the carbanion of certain ally1 silyl ethers [134]. methylation

equivalents

when R=t-butyl (y:u=89:11)

result

(i.e.,

anion

like

the ratio

formed

The latter

Even higher

halides

CL1 and CLII;

than when R=THP (y:cr=54:46) [132]. [133].

as homoenolate

Thus,

y:cr=97:3.

s-C4HgLi THF -65”

’ R’

CL

CL1

CL11

Conjugate additions of acyl carbanion equivalents via protected cyanohydrin have been described CL111 to

[135] _

The procedure

is

illustrated

by the

conversion

of

CLIV.

L/f”

‘r-

i

.+

H

il

cl I

\

I

H2°

O--r

Direct

formation

of

the

carbonyl

anion

of

diisopropylformamide

(CLV) has

39

been achieved

at -78O; CLV was trapped with benzophenone to give

yield

The work demonstrates

[136].

In a different

proton abstraction. gas-liquid

chromatography

an intermediate carboxylic

acids

Li e N(i-C3H7)

anion can be formed by

study,

has been found using radio-

of this

evidence

anion of ethyl

ester

with certain

for-mate (CLVII) is dilithio

salts

PH

8 ii COC2H5

(C6h5)2C-fN(i-C3H7)2 0

2

CLVI

The dilithio Thus, reaction

of

[137]_

CLV

are cyclized

that a carbonyl

that the carbonyl

in the reaction

CLVI in 92%

salt

of propiolic

acid

of CLVIII with epoxides by acid to lactones

(CLVIII)

affords

like

SH

CLVII acts

as an acyl

6-hydroxyacids

synthon

like

[138].

CLIX which

CLX.

-I

9

CH3CH2CHCH2CSOH 0

H5C2 CLVIII

CLIX

Lithiocarbamate of aldehydes like

[139].

CLX

CLXI has been shown to be a useful

It is suggested

CLXII, and that the thiol

reagent

that CLXI is more stable

group is more easily

for

the synthesis

than carbanions

removed in the former than

in the latter.

Li

s

II

CH3SCHSCN(CH3)

CLXI

References

p. 95

2

CH3&R CLXII

40

.Several tri-

papers have described A full

and dithianes.

electrophiles synthesis

paper describes

of lithio-1.3.5trithianes

of aldehydes

since

CLXIV with either

E-butyllithium

of CLXV by RX followed

Treatment of salt

Conversion

anions like

or lithium

of CLXVIII with diethyl with 3% copper

CLXVII

methylmalonate

gives

like

CLXVmay now be considered

affords

by treatment [lSl]. products

L-1421.

of

Alkylation like

CLXVI.

CLXVI

diisopropylamide

Michael acceptor

with

Their use in the

CLXV

CLXVII with lithium

of

of alkylidenedithianes

diisopropylamide

conveniently

Salts

and reactions

CLXIII [140].

prepared in high yields

by hydrolysis

as a two-carbon

of lithium

the preparation

CLXIV

CLXIII

which serves

acyl

CLXV is conveniently

chemistry

like

is demonstrated.

CLXIV to masked cr,&unsaturated general

additional

gives

For example,

CLXVIII reaction

CLXIX which is converted

to CLXX

sulfate.

CLXVIII

41

A convenient preparation of cr-oxoalkanoyl-1,3-dithianes (CLXXI) has been described,

[143].

These compounds, in turn,

involving

an intramolecular The sequence

nones.

Wittig

reaction

is illustrated

are used in a new synthetic route to afford

substituted

by the preparation

cyclopente-

of dihydrojasmone

(CLXXII) in 70% yield.

Li FN n-C5H17C(OC2H5)2 J THF -78”

4%HCl 25” ’

CLXXI

1. LiN(i-Pr)2,

THF

2. (C6H5)3P)=Br+

l+3= n-C5?1

D

Raney Ni

I JI 0

CLXXI I

Finally,

dithianes

as illustrated

for the conversion

particularly aliphatic

have been employed in the preparation

useful

for

of CLXXIII to CLXXIV [144].

the synthesis

of cyclophanes

of cyclophanes The method is

with functionality

in the

bridges.

Lithiation of practical

of Schiff

intermediates

p-nitrobenzaldehyde

Rekrencesp.95

Schiff

bases and enamines continues for

synthetic

bases of

purposes.

to provide

a rich

Thus, epimerization

6a-aminopenicillins

source of the

and 7a-aminocephalo-

42

g-C4HgLi

Ni

\

)

H2Br

CLXXIII

sporins

with

phenyllithium

kinetically syntheses the

controlied of

of

conditions

an ion

by protonation has enabled

inactive

pair

[745,146-j.

trans-CLXXV

successful

because

with

acetic

the completion

and cephalosporins

the

is apparently

nMF affords

followed

penicillins

conversion

series

CLXXIV

to

whose configurational

of

C6H5Li -78”

cis-

lithium

memory is

ArCH=N

of

under

new total

An example

the active

treatment

acid

illustrates

isomer. salt

The

CLXXVI with

lost.

CLXXVI

?

I

DMF

CH~C~H~ trans-CLXXV

CH3C02H

ArCH=

’ H20, THF

cis-CLXXV Two papers hydrolysis,

have described

mono-a-alkylated

CLXXVI and 4-bromo-1-butene butane

afford

CLXXIX.

alkylations aldehydes give

of

Schiff

[147,148].

CLXXVII while

bases

to afford,

For example,

after

carbanion

CLXXVIII and l-bromo-4-chloro-

43

c

-H (CH ) C’ 3 2 ‘(cH~)~cH=CH~

,c_H\

(C~3)2C-~;---+t_-C4H9 Li+

CLXXVII

CLXXV I

0

ci

(~H,),lh

CLXXVIII

Other papers have described similar reactions leading to mono-a-alkylated

For example, treatment of CLXXX with 2,3-dichloro-1-propene

ketones [149,150].

affords,

after

transformations

1,4-diketone

CLXXXI which is a precursor to dihydro-

Use of optically active Schiff

(CLXXII) [149].

jasmone

these

hydrolysis,

leads

to optically

active

has thus been prepared with an optical

!YC6”, 3 \C C” /--Ah” 2 -+ Li

respectively intermediates to aldehydes

p. 95

CH

z3

‘6”5bgdH N

0

CLXXXII

CLXXXI

enamines are 3-oxocarbanion to its

lithium

and benzaldehyde [151].

Metalation

which also [152,153].

gives,

equivalents.

salt after

of ally1

For example,

CLXXXIVwhich upon treatment hydrolysis,

amines like

have been alkylated Thus, butylation

mostly CLXXXVIII hydrolysis Ret-erences

of 26% [150].

C6”,3C(CH2)2CC”3

CLXXXIII is converted methyl iodide

CLXXXII in

2-methylcyclohexanone

% B

0

CLXXX

Metalated

purity

ketones;

bases like

of which gives

enamine with

CLXXXV and CLXXXVI,

CLXXXVII afford

and, in some cases,

of the lithio n_-heptanal.

salt

similar

hydrolyzed

of CLXXXVII gives

44

"1 ,C=C,

A”3

A

'6"SCH2

E-C4HgLi

H 65

\C H

>

0" .

1

CH31

I

.

HCl

C6H5FHCH2CH

1

C6H5CH0 "20,

A

0 II

CH3

CLXXXVI

CLXXXV

cLxxxv111

CLXXXVII

Regioselective and

nitriles

stitution CXC

Such

[154].

at or near

to CXCI

realized

y-alkylations

as

in good

the

reactions y-carbon

yield.

illustrated

are

and

(CXCIV)

trapped

by the

chlorotrimethylsilane

at

have atom;

low

conversion has

CXCV

been

on enaminoketones,

found

CLXXXIX

alkylations

are

of CXCII

[155].

and

methanol-O-d, Upon

sub-

is converted also

via

conveniently

to CXCIII.

lithiated

with

esters,

to be insensitive'to

example,

been

temperatures

to give

realized

for

Intramolecular

N-t-Butyl-3-methyleneaziridine banion

also

warming

the

resulting methyl

to >-50",

car-

iodide, CXCIV

CHSI

\d

0,

O‘u

3% I

C6H5v -w-A&

SH5-/

CXCIII

CXCII

dimerizes aldehyde sine

to CXCVI. [156]

Lithio

salts

and a ketone [157]

and cembrene,

of enamines have also

been reacted

as a part of the total

syntheses

with an of maytan-

respectively.

Ic

I

Li

-4

+HNKY Y

cxcv

CXCIV In connection

with

cycloaddition

CXCVII has been reacted cycle

with

CXCVIII in 65% yield

with unmetalated low yield.

References p_ 95

starting

Similarly,

material

ally1

reactions

azobenzene

[158].

CXCVI of

to afford,

ally1

anions,

after

hydrolysis,

In the absence of azobenzene, to afford

cyclopentane

lithium

salt

hetero-

CXCVII reacts

derivative

CXCIX in

anion CC has been condensed with cr,B-unsaturated

46 esters

to give

CC1 in good.yield

CXCVIII is thought

to involve

[159].

Though the cyclization

a two-step

process,

that leading

leading

to

to CC1 is thought

to be concerted.

2

SC6H!i

cc1

cc A large sulfur

number of papers have appeared dealing

atoms.

Thus, two new cyclopropyl

have been prepared ketones

[ 1603 _

the conversion

phenyl sulfides,

from lithiocyclopropyl

Such compounds are useful of cyclopropyl

OH

cc11

with lithiation

to cyclobutyl

phenyl sulfide

CC11 and CCIII, and appropriate

in the spiroannelations systems.

CYto

involving

1,2-Dianions tive

metalation

of mercaptans like of thioketones,

benzyl mercaptan [161]. electrophiles

to afford

CCIV, previously

have now been synthesized

Dianion CCIV has been condensed with a variety

of

either

CCIV

ccv

dithiocarbamates

can be converted reacted

in a stereoselective the reaction

f C6H5CHSE CCVI

synthesis

of dl-C17-Cecropia

of lithiosulfide

of other

juvenile

CCVII with bromide CCVIII [162].

(CCIX) have been alkylated

to u,&unsaturated

with a variety

on the stoichiometry.

CCV or CCVI depending

C6H5LHSH

Lithioallyl

reducof

:’

normone involved

by

by metalation

C6H5-CH-SLi

A key step

only prepared

aldehydes

to afford

[163,164].

CCX which

Salt CCIX was also

electrophiles.[l63].

SC6HS

CCVII

A general useful invoives References

synthesis

in prostaglandin regioselective p_ 95

CCVIII

of 1-alkyl-1-cyclopentene-cis-3,5-diols, preparations, alkylation

has been described of dianion

compounds [165].

CCXI followed

The method

by isomerization

and clesvage have

with

triethylamine

to afford

CCXII;.a

variety

of alkyl

been employed.

OLi g

0 T

= P lp

p

RX 2. H20’ 1.

iH

K2H5&N

4C6H5

CCXI

CCXII

Other dilithio in synthesis. to give

several

salts

of sulfur

Thus, dilithio

salts alkyl

benzylation

containing

salt

to y-substituted

of f3-keto sulfoxides halides

as a route

of CCXVI followed

with aluminum amalgam affords

compounds have also

has been reacted

CCXIII

CCXIV which are converted

Oialkali

yield

halides

like

CCXVI

have been alkylated

elimination

the methyl vinyl

with various

Aor,B-butenolides

to ketones and aldols

by reductive

been used

[1.67,168!.

epoxides

(CCXV) Cl64 with For example.

of the sulfoxide

moiety

ketone homologue CCXVII in a

of 75%.

Li C6H5SCHC02Li

R’ CCXIV

CCXIII

ol 0

‘0

ccxv

Na

//~_/-~6~5

C6H5SOCHCOCH2Li

b’ CCXVI

CCXVII

A new synthesis reaction

of the

of allylic

lithio

CCXX in good yields

salt

11691.

sulfones

of ally1

has been described

alcohols

Elimination

like

which involves

CCXVIII with CCXIX to afford

of the SO2 moiety from such sulfones

49

using potassium

and carbon tetrachloride

hydroxide

the preparation

vides a facile method for

Dianions

have also provided

of sulfones

or via dilithio

of polyolefins a novel,

salts

pro-

such as $-carotenes.

versatile

method of preparing

small ring systems as illustrated by the conversion of CCXXI to CCXXII [170].

ccxx

CCXIX

CCXV!II

2E-CqHgLi

fi-C4HgLi

2CHgI

LiAlH4

THF, -80”’

’

CCXXII

The first 11711.

Darzens synthesis

The success

thiol

esters

has been described

of the method depends on the use of a-bromothiol

non-nucleophilic

bases,

CSHSCHO+

E

Several

of glycidic

and polar,

LiN[Si(CH3)

BrCH2 S-t-C4Hg

papers dealing

aprotic

THF, 0” with regiospecific

I,

An example follows.

/“\ p Hzo3 CSHSCH-CH S-t-C4Hg

)

reactions

By employing

al dehydes , methyl alkyl

ketones

have been caused to undergo aldol

via the kinetic

enolate

[172].

from a,&unsaturated

References

p_ 95

ketones are similar.

reactive

of ketone enolates

have appeared in 1974.

lithium

highly

solvents.

esters,

electrophiles

An example is shown.

such as condensations

Kinetic

enolates

LiN(i-C3H7) THF -78"

% Li+

i,

'sH5

Other regiospecific

ketone enolates generated by treatment of enol acetates

or siiyl ethers with organolithiums have been reacted with a variety of electrophiles.

Thus, for example, treatment of CCXXIII with formaldehyde gives CCXXIV

in high yield [173]. Compound CCXXIV and related ones are particularly useful for Michael condensations, annelations with B-ketoesters, chain extension with cuprates, and Diels-Alder reactions. Enolates like CCXXV have also been reacted with y-iodotiglate esters and silanes to afford compounds like CCXXVI [174,175]. The y-iodotiglate compounds serve as masked ketoalkyl groups. Finally, enolates like CCXXIII have been treated with a-silylketones like CCXXVII to eventually give ketones like CCXXVIII [176,177-j.

Y

Q

LiJZD

CCXXIII

CCXXIV

Li

ccxxv

a-Lithio salts of esters continue to be studied. A new synthetic conversion of silylesters to a, B-unsaturated esters in high yields has been described [178]. Thus, CCXXIX with benzaldehyde gives ethyl cinnamate (E:Z=3:1) in a

ccxxv I

CCXXVII

ccxxv111

(G = Si(CH3)3 or C024-C,H9)

The method is better in some cases

yield of 84%.

the Emmons-Wadsworth-Horner procedures. tones

(CCXXX) from a-methyllactones

lithium which,

and bromination upon treatment

procedure

on trans-lactones

phenyl disulfide latter

gives

lithium

salt

A new route

involving

with 1,2-dibromoethane with base,

to afford

trans-CCXXX.

give

involves

CCXXXIII unexpectedly

lithiation gives

treatment

affords

or

with triphenylmethyl-

bromolactones

like

CCXXXI

[179].

A related

of the lithiolactone

with di-

Oxidation,

treatment

the Wittig

to a-methylene-y-butrolac-

CCXXXin high yields

CCXXXII [lSO]. Finally,

than either

then heating,

of estrone

heterocycle

of the

methyl ether with CCXXXIV [lSl].

,---,= I9 =

Li (CH3)3SiCHC02C2HS

=o

,..--_ =_

bit-

CCXXIX

ccxxx

ccxxx I

52 it has been found that N-unsubsti-

In the area of a-lithiocarboxamides. tuted

D-lactams with E-butyllithium

afford

dianions

like

CCXXXVthat undergo

reaction with alkyl halides and ketones to afford species

It should be noted that the acidity lactams

of the carbon-hydrogen

is not enhanced by an additional

functional

as in CLXXV. Lactam CCXXXVII has similarly alkyl

halides

The latter

contrasts-with

is interesting

related

Another a-metalated dl -vincamine dialkyl alkyl

reactions

group like

the C-silylation

of lactone

enolates

N,N-Disubstituted

derivatives

are metalated

proceed

by lithium

on the a-carbon

‘6%

acetamides

base of

CCXXXVIII [183].

product

obtained

which afford synthesis

and their

diethylamide;

as expected

a Schiff

with a variety

to afford

lactam has been used in the total

[184].

halides

since

CCXXXVI[182].

bond of such

been alkylated

and with chlorodimethylphenylsilane

reagent

like

0-silylation. of the alkaloid

a-alkyl

and a,a-

alkylations

with

[185].

‘6”5

E

Li

ccxxxv Metalazion useful _ give

CCXXXVI

of phosphorus-containing

Thus, a new one-step

derived

CCXXXVII

a,6-unsaturated

compounds has also

carboxyvinylation acids

CCXXXVIII

been syntheticall.

of an aldehyde or ketone to

has been described

[186].

For example,

treatment of dilithio salt CCXXXIX with cyclohexanone affords CCXL in good yield.

An efficient

ketones

to a-ally1

treatment are reacted

of salt

one-pot aldehydes

procedure

for

the one-carbon

has been reported

CCXLI with a ketone to afford

with ally1

bromide;

hydrolysis

gives

[187].

homologation

of

The method involves

enamines like aldehyde

CCXLII which

CCXLIII.

53

0 ii

=

8

,CO2"

-r;H-P(OC,H,)2 'H

Li

CCXL

CCXXXIX

CCXLI

CCXLII

CCXLIII

A new method for the stereoselective synthesis of trans-olefins has been described which involves alkylation of salt CCXLIV and reductive cleavage of the resulting alkylated ester to afford, for example, CCXLV [188]. The cleavage of HMPA by organolithiums effected at lower temperatures and longer reaction periods than previously described gives rise to mixed secondary amines by attack of the organolithium on N-methylmethyleneimine [189]. Dilithio salts of aminophosphonamidesCCXLVI have been alkylated forward

products

like

to give

either

straight-

CCXLVII or cyclic ones like CCXLVIII depending

upon

conditions [190].

Li CH,CH=CHCHP(OC,H,)2

&,,C5"5

'b CCXLV

CCXLIV

I (C,H,o$[-N

LY---lNR Li

0

0 R' CCXLVI

References

(C2H50) $,-yNR

p. 95

CCXLYII

RI

C2H50P;'z Ii N O .4 CCXLVIII

54

A new synthesis addition

of P-aryl-

of a-lithioamides

has been described

P

by means of an intramolecular,

and P-vinylindoles [191].

An example

follows.

Cl LiN(i-C3H7)

C-C6H5

3

THF -78” YCH2C6H5

Hi: 'C 0

H 65

A new method to dehydrogenate An example

is

shown on anthracene

metalation of CCXLIX (R=t_-butyl,

ring

derivative R’=CH9)

species affords only trans-CCL [193]. ethyl halides gives only a-CCXLIX

2 n-C4H9Li TMEDA hexane A

CCXiIX

’

systems

has been demonstrated

CCXLIX.

In another

study,

[192]. mono-

followed by alkylation with various

In contrast, alkylation of CCL1 with

(R=R’=C2H5).

H 0‘ GP

H

,&-C4H9 +

0

0 *+"H

‘0

@?.

H C2H5 CCL1

CCL

A highly stereosel ective

Lit

, completely

regiospecific method has been re-

ported for dehydration of B-hydroxyesters [194].

H

COX2H5

/’

h

Rl

An example is shown.

2

Treatment of epoxide CCL11 with lithium diisopropylamide, silane, and acid gives cyclopentanone CCL111 [195].

chlorotrimethyl-

In contrast, use of-lithium

pyrrolidine in the reaction sequence affords cyclopentanone CCLIV.

These re-

sults represent the first example in base induced epoxide ring openings where kinetic versus thermodynamic contrc? determines the orientation.

Refe&es

p. 95

56

CCL11

A new (R=H

.

CCLITI

preparation

or CH3)

has

been

1-azabicyclobutanes

achieved

CCLVI

example

of a small

ment

ketone

of

of certain

ring

CCLVIII

are

this

x

Carbon ---

Metalation

of methyl

CCLIX

are

that

ketones,

converted

acyl and

vinyl anion

by methanolic

l,+dilithio-1,3-butadiyne at

base

-55" , and

ether

halides

and

The

(CCLXII) with

first

has been achieved by treat-

[197].

related

CCLVITI

compounds

acid

chlorine

in ether

like

prepared

like

with

CCLX

[199].

that

CCLXI.

by treatment

in Freon-11

at -55"

compounds

of CCLIX

ethers

to ketones been

gives

Reactions

substituted

have

molecular iodine

C1981.

give

hydrochloric

molecular

[196].

at Nitrogen

equivalents

l,&Dihalo-1,3-butadiynes

bromine

(CCLVII)

same

CCLV

of 2-methyl-substituted

CCLVII

and

alkyl

P-vinylaziridines

diisopropylamide

CCLVI

6. At &and

aldehydes,

lithium

dehydroannulene

CCLV

like

N-unsubstituted

by treatment

with

with

CCLIV

at Two

-8O", papers

of liquid have

57 0CH3

/OC"3

/ 7

-7

1.i

the

acetylenes CCLXIV

II CH-E 3

E

CCLXT

CCLX

CCLiX

described

0

__;'

synthesis

The

[200,201].

with

of

[14]-annulene

derivatives

syntheses

begun

are

(CCLXIIT)

by condensing

g-Methylanisole mixtures

the

carbonated

with

the

References

anisole

p. =a

Sincethe

authors

agent

CCLXV

has been

a-metalation[202].

metalating

like

CCLXIII

CCLXIV

lithium,

species

lithio-

CCLXV.

CCLXII

reaction

using

conclude

is more oxygen

reacted to measure amount that

important atom.

with the

-n-

and

-t-butyllithium

relative

of g-metalation the

relative

than

steric

and

amounts

of g-

is higher

with

oligomer hindrance

size

the

versus t-butyl-

of the

to coordination

58 1. RLi 2. co2 ) 3. acid

PCH3

i-

H3

H2C02H

Other authors believe that steric effects of the y-carboxamide stituents of CCLXVI are responsible

rather

for

lithiation

than at the 2-position Gf this molecule

resulting

organolithium

with ethylene

oxide

occurring

[203].

gives

sub-

at the 4-

Treatment Gf the

CCLXVII. 0

g-C4H9-HNOC ’ < 0

1’

CONH-&-C4H9 CCLXV II

CCLXV I Two papers have described

the interaction

E- and t-butyllithium

[204,205-j.

evidenced

with chlorotrimethylsilane

lithium

by trapping

affords CCLXVIII only

temperatures giving

(-78”)

at

t-butyllithium

of 1,3,Strifluorobenzene

Though E-butyllithium

low

to give

temperatures

enters

into

affords

with

metalation

as

CCLXVIII, t_-butyl-

(-115O).

At higher

a substitution

type reaction_

CCLXIX in good yield. F

C(C”3)3 I

C(CH313

CCLXIX

CCLXVIII In contrast benzene affords carbonation isolated.

to previous

reports,

lithiation

only the 2- and 4-lithio

[206].

None of the previously

of m-di(trifluoromethyl)-

derivatives described

as evidenced 5-lithio

by

isomer could

be

59

z-C4HgLi

,

&I3

+

$CF3

CF3 Li

The first

application

removal of the directing reported C2071.

of sequential group to give

directed

metalation

1,3-disubstituted

followed

ferrocenes

by has been

An example is shown.

H3 (C6H5)2C0

Na/C6H5CH3

100”

Fe

’

Fe

00

0 0

Two phosphorus substituted

ferrocenes

have also

ferrocene

CCLXXhas been prepared by treatment

ferrocene

by chlorodiphenylphosphine;

asymmetric catalytic phosphine

oxide

which undergoes

hydrosilylation

has also

been dimetalated

condensation

of the corresponding

CCLXXis useful of ketones

with a variety

been described.

[208].

as a chiral Diferrocenyl

by E-butyllithium

Chiral lithio ligand

in

phenyl

to give CCLXXI

of electrophiles

[209].

CCLXXI

. References

p. 95

60 Finally, be fruitful

decomposition _

The first

of tosylhydrazones

case of effecting

vinyl

by organolithiums deuteration

(CCLXXII to CCLXXIII) which apparently

previously

mechanism [210].

of fluorenone The smailest tion

has now been shown to proceed paracyclophane

a ring current

via a

of the tosylhydrazone

via a carbanion

intermediate

despite

f211].

by decomposi-

the high degree

[212].

&

f-6 JNNLiTS

1’ _._. __

CCLXXII

Decomposition c4.2.0.0

proceeds

to date (CCLXXIV) has been prepared

of CCLXXV; pmr of CCLXXIVreveals

of strain

Decomposition

to

from a tosylhydra-

zone has been described unrecognized

continues

butane [214],

CCLXXIII

of tosylhydrazones

2,4.03*5]oct-7-ene

benzobullvalene

/D

[213],

has also

given rise

to tetracyc’io-

bicyclo[2.2.1]hepta-2,5-dien-7-spirocyclo-

[215],

and five

new bicyclic

methylenecyclopropane

[216].

V. Heterocycl es Reinvestigation salts

like

of the reactions

of phenyllithium

CCLXXVI (R=H) has demonstrated

with thiopyrylium

that such reactions

give oligomeric

61 materials

rather

In fact, giving

40°

sulfide

Such

A full

[2191.

(CCLXXVII, related

R=phenyl,

synthesis latter

(CCLXXXI)

On the

other

CCLXXVIII

(CCLXXIX)

the

R'=methyl)

from

method

has

of which

synthesis salt

in the

ring

R'=phenyl) system

lithium are to

occurs

with

or sodium

stable

[217].

earlier salts

in solution

be pyramidal

at

to

sulfur

and t-butyllithium,

R'=methyl)

has

example

appeared

and

[220].

the Use

of a selenabenzene

L-2211.

R

R

\

,'I +

R

/ 1' (7

Clo,

I

R' CCLXXVII

CCLXXVI

: ’ ‘5,R’ 02

H5C

I

R

CCLXXIX

A new, example

References

direct

is shown

p. 95

synthesis [222].

of

of 1-methyl-3,5-diphenylthiabenzen

CCLXXX

first

(R=h,

in agreement

the

been found

(R=phenyl,

resulted

hand,

with

some

have

describing

of CCLXXIX

CCLXXVII

sulfur-containing

thianaphthalenes

paper

like

of the

of salts

thianaphthalenes

[218]_

0

thiabenzenes

intermediates-

deprotonation

give

of the

stable

extensive.degradation

workers, DMSO

than

of oxazaphospholidines

has

been

described.;

an

62

i””

0 C2%0,

p3

(CH3)z,/~+F6H5

Metalation

to

R-!-R’ -75”

of side

chains

II -+cza 0

of various

‘gH5

(CH312N

)

Dianions like CCLXXXII

in synthesis.

2P

heterocyclics

of certain

R’

continued

pyrimidines

and

to find

use

related

Com-

have been condensed with alkyl halides, ketones, and other electrophiles

pounds

to give compounds like quinolines solvent

and

kinetically opposite

pyridines Thus,

[224]. and

CCLXXXIII [223]. have

been

CCLXXXIV

found

solvated

a thermodynamically

is realized

with

Selective

metalations

to be strongly by THF

of dimethylated

affected

or by ether

by choice

is formed

by a

process, respectively.

controlled

of

The

CCLXXXV.

Li CCLXXXI

I

CCLXXXIII

Temperature the

metalation

L-225,226]. inately

and of

Thus,

on the

(R=methyl)

to give

at the

(R=CH3)'is

at 25".

Interestingly, gives

have

of CCLXXXVI

metalation

compound

temperatures

effects

been

CCLXXXV

found

2-methyl-4-substituted-1,3-thiazoles

ring

occurs

substituent

CCLXXXIV

P-methyl

stable

mostly

CCLXXXVII

at

initial

group

-78",

similar

to give

it couples

metalation

CCLXXXVIII.

and

(R=phenyl)

while

to

at -78" reaction

CCLXXXVIII. with

be important related

compounds

proceeds

predom-

of CCLXXXVI Though

unmetalated

of CCLXXXVI

in

(R=phenyl)

the

latter

heterocycle at

higher

63

I \ iL\

9-i

\S/--”

CCLXXXVI I

CCLXXXVI

Lithio-2,4,4-trimethyl-2-oxazoline

ccLxxxv111

(CCLXXXIX) continues

to be alkylated,

then decomposed with aqueous acids or alcoholic sulfuric acid to give carboxylic acids or esters, respectively [227].

has been shown to be highly pentane carboxylic

acid

Use of 1,4_diiodopentane in the sequence

stereospecific

[228].

leading

to mostly

cis-2-methylcyclo-

The use of the lithium salt of chiral oxazoline

CCXC leads to optically active carboxylic acids [229,230].

Either R or S di-

alkylacetic acids can thus be prepared depending on the order of addition of

RX and R’X.

Treatment of CCXCwith racemic

stereoselective of R-enriched

alkylation halide

of the S-enantiomer

[231].

optically

The use of benzaldehyde Finally,

acids.

active

obtained by such reductions

30-40X

and allows

reducing

recognition. then

respectively

aluminum hydride

agent of ketones

have exhibited

recovery

[232].

in the latter reactions gives cinnamic

of CCXCwith lithium

optical

purities

gives

[233].

ate com-

Alcohols

ranging

from O-5-65%.

\

kN&CH2Li

CH2Li

ccxc

CCLXXXIX

Reactions References

or 6-methoxyacids,

or phenyl ketones

treatment

of chiral

gives

by water or by methyl iodide

6-hydroxy-

plex CCXCI which is a new chiral

I -0

followed

iodides

of the halide

Thus, CCXC is capable

Treatment of CCXCwith aldehydes water affords

set-alkyl

p_ 95

of the lithium

salts

CCXCI

CCLXXXIX, CCXCII, and CCXCiII with epoxides

64 give

the y-hydroxyl

mineral

acid,

afford

CCXCII with esters resistant

derivatives

butyrolactones and nitriles

to reduction

as precursors

in high yields

gives

which,

A

Reaction

of the oxazine

first

reported

phosphole

f 0

CH2Li

been described

formation

of phosphine CCXCIVhas resulted

of a phosphatriptycene

CCXCVIand subsequent

[238].

Products

arising

CCXCVI are obtained

with aldehydes

pounds are realized

with esters

go

(CCXCV) [237].

condensation from reaction

0” 0

of

have

at the methyl group of

and ketones while ring Z-substituted

com-

H3ceH3 !Gf 16H5

1

CCXCVI

ccxcv

to prev.ious results,

to undergo both ring and side-chain as evidenced

Metalation

and carbon dioxide.

CCXCIV

In contrast

in the

with electrophiles

* I

CH2Li

CCXCIII

and aryne formation

sulfide

that are

[236].

CCXCII Metalation

of

such compounds thus do not serve

a

N’

on treatment with

[234,235].

keto derivatives

by sodium borohydride;

to aldehydes

s

of the heterocycles

by carbonation

2.5-dimethylthiophene metalation

by lithium

to give CCXCVII in low yield

has been caused diisopropylamide [239].

Similarly,

65 5-methylpyrimidine

afford

CCXCVIII.

metalated sented

has been ring metalated Even pyridine,

and condensed with benzophenone to

quinoline,

and isoquinoline

by the above base at low temperature.

that 2,3-dialkylpyrazines

N-methylpyrrole

Evidence has also

can be ring-metalated

can be o!. B’-ring-dimetalated

apparently

[240],

are

been pre-

and that

to give CCXCIX by organolithiums

[241].

Li

gyH3

I \ l-4

CCXCVI I

A variety by metal-halogen

CCC1 [243]

derivatives

exchange or by metalation

have been converted

to 2-substituted

[244].

CL.CL’-Diiodothieno-[2,3-blthiophenes

from the corresponding

thieno-[2,3-blpyridines

lithiated

derivatives

CCCIV [246] and CCCV [247]

with a variety

have been prepared

and tetrabromo dilithiated

derivative compounds.

is now available (CCCIII) are readily and iodine

have likewise

[245].

via CCC11 synthesized Thiophene de-

been dimetalated

and reacted

of electrophiles.

Br Br

ccc Referencesp.95

ccc1

either

and the compounds condensed with

to the corresponding

A route

rivatives

CCXCIX

of thiophenes

Thus, dibromo compound CCC [242]

electrophiles.

& H3

ccxcv111

of lithiated

Li

N’_

‘N*C(C,H,)2 1 bH

ccc11

66

ccc111

Several reactions dine

papers have been concerned

.of pyridines

reduced derivatives phenyllithium, non-Friedel

[248].

or addition-elimination

of as many as six different

certain

organolithiums

chloride this

gives

and various

from pyridine

heterocycle

heterocycles

[249].

by coupling

[250,251].

The method

of CCCIX.

Ar-C

\

AL cccvI

II

I

Li

O@C\Ar CCCVII

a

The linear

0

Li,

and

CCCVIII and represents

arenes has been achieved

with nitrogenous

by the preparation

adds to pyri-

to 2,6-di-t-butylpyridine

method of acylating

linkage

is illustrated

addition

Treatment of CCCVII, derived

with -p-ethoxybenzoyl crafts

with

Excess t-butyllithium

and pyrimidines.

CCCVI which decomposes

to afford

cccv

CCCIV

CCCVIII

‘6”5

67 The first

substantiated

has been reported

[252].

with lz-butyllithium reaction

reaction

of a-lactams

Thus, treatment

at 25” gives

of CCCX (Rl =g-butyl

ring-opened

product

II Rl H

axial

In contrast,

P”

Rl b

CCCXI

CCCXII

Organolithiums

have been added to sugar lactones

CCCXIII [254]

and to 0x0 sugars to give alcohols

direction

give an alcohol

R’CbHNHR2

Rl

-R2

reactions

at -78”

[253].

t-C4Hg-F-CH=NR2

cccx

latter

CCCXI.

, R2=adamantyl)

of this same a-lactam with various organolithiums (R’Li)

gives a-aminoketones CCCXII in good yields

like

with an organometallic

are stereospecific-attack _ Methyllithium

to afford like

sugar lactols

CCCXIV [255].

of the nucleophile

occurs

has been added to an oxocyclopentanone

which is dehydrated

to afford

The

from an to

the novel methylidenedihydrofuran

(CCCXV) [256] _

bfz CCCXIII

VI.

Addition

CCCXIV

and Substitution

Reviews in this References p. 95

area include

cccxv

Reactions a discussion

of carbanion

additions

and

68

cyclizations

involving

carbon addition

complexed with tertiary

and as initiators

hydrocarbons carbonyl

o complexes [257]

for

and olefins

the telomerization

[260]

active

A novel

alcohols

have been described.

cated

with aromatic

Reactions

of prochiral

complexed with diamines to give

building block system for the preparation of ketones from vinyl

is illustrated FSi

initiators

have been reviewed [261].

silanes has been described [262]_

process

of ethylene

carbon-

The use of

amines as polymerization

compounds with organolithiums

optically

and base-catalyzed

of hydrocarbons 2nd related compounds [258].

organoalkalies [259],

anionic

is

Several routes are presented and the

by the preparation

of CCCXVI from the components indi-

(CH3)3Si).

71

+d-

f H2C@

t-C4HgLi

(GSi )3CLi

\

H2C0

CCCXVI

(_-3i)3CLi

CH20

-

(=Si)2C=CH2

l

Li

+

z:,‘;u-

H2C0 hydrolyze

CCCXVI

1

epoxidi ze -=>q

Synthetically CCCXVII followed

useful

addition

by cyclization

of E-butyllithium

of intermediate

CCCXIX; CCCXVIII has been trapped

to unconjugated

CCCXVIII has given

by formaldehyde

[263].

triene cyclopentane

The use of the con-

69

jugated

triene,

substituted

2,7-dimethyl-2.4,6-octatriene,

cycloheptadiene.

to conjugated

Allyl-

enynes to afford

in this

and n-butyllithium

terminal

acetylenes

reaction have also

[264].

t-Eiutyll i thium has been shown to add to trans-cyclooctene CCCXXand cis-cyclooctene cis-Cyclooctene conditions.

fails

in yields to react

n_-Butyllithium

Such additions

with t-butyllithium

to methoxy derivatives

is lost

derivatives products

under the same reaction

like like

CCCXXI afford

alcohols

allenes

CCCXXIII with lithium

CCCXXI

11‘C3Hit=C=c,CH20H CH3/

/\ //// G-

’

gzCzH!i CCCXXIV

‘n-C -

CCCXXII

,C0ZCZH5

References p_ 95

acetylide

(CCCXXIV and CCCXXV)where the

? CH3 -EC-CH20H C”3

cccxx111

like

[267].

~c~H7-f

cccxx

[265].

has now been shown to add to propargylic

Treatment of azulene

substituent

to afford

of 89% and lo%, respectively

give abnormal 4- and 6-substituted chlorine

been added

cccxv111

CCCXVI I

CCCXXII.

a

A$+

LAf

[266].

gives

cccxxv

H 49

70

A new synthesis

olefins

of

cyclohexanones

has been described

+

H3CO

[268].

o II

from dianions

An example

of

f3-diketones

and nitro-

follows.

i

o II

v+ acid

CH3CifZCCH2Li _$$?

H3C0 6CH3

Lithiosodio

carbonyls actions alkyl give

salts

to give 12691,

[270].

annelating of

wtih

al kyl

Al kylation

of

by oxidative

reagent

CCCXXVI with

acetylacetone

acetoacetate

(CCCXXVI) have been added

like CCCXXVII which

COIIqXWIds

CCCXXVIII followed

Treatment

methyl

and al kylated

derivatives

a useful

of

in the

ha1 ides

are

to give

CCCXXVI with

elimination preparation

an equivalent

useful

of

re-

in annelation

the expected

terminal

iodomethylthiophenol

affords of

t0

3-oxo-4-pentenoate,

terpenes

methyllithium

to

and alkaloids interestingly

[271]. gives

[272].

C6H5S &02CH3

cccxxv11

CCCXXVI

Bromomethylsulfides o-methylene

derivatives

illustrated

with

cccxxv111

have been used as formaldehyde of

ketones

dilithiophenylacetic

and carboxylic acid.

acids

equivalents [273].

to prepare

An example

is

71 C6H5CH2SCH2Br ’

Li C6H5CHC02Li

H5C63

NaI04

..4

OH

‘s+ As part

of

a study

to develop

nucleophilic

aromatic

reacted

with

chromium tricarbonyl

The process

[274,275-j. the

certain

chromium moiety

tricarbonyl mediates

complex

is

substitution,

illustrated

of cc-pyrone

to activate

various

OH

complexes

iodine.

(CCCXXXI) with

rings

aryl

organolithiums

have been

of

benzenes

substituted

by the conversion

can be removed with

‘sH5

H 65

new techniques

towards

>

A

Similar

of

CCCXXIX to

reactions

organolithiums

CCCXXX;

on the

iron

give

inter-

(RLi)

1 i ke CCCXXXII which, upon acylation, afford CCCXXXIII [276] _

C(CH3)2CN i

CCCXXIX

cccxxx

CCCXXXI

CCCXXXII

Two new methods Sulfenylatior which,

preparing

and selenylation

upon treatment

Treatment

of

CCCXXXIII

of

Referemes p. 95

with

of

a,B-unsaturated a-lithionitriles

hydrogen

lithio-a-silylpropionitriles

nitriles

peroxide,

give

ha-re been

reported.

give

compounds

like

final

product

[277].

(CCCXXXV) with

esters

also

CCCXXXIV

affords

72

u, B-unsaturated nitriles

like

thiophenyl

nitriles

Finally,

[278]_

CCCXXXVIwith NBS results

moieties

by a carbonyl

oxidative

decyanation

in the replacement

of secondary

of the cyanide

group [279].

SeC6H5

I

_.‘lCN

and

CN

N

‘sH5

C6H5

Li cccxxx1v

cccxxxv1

cccxxxv

Phenols may now be prepared

from aryl

chlorides

or bromides in yields

34-80% by adding them to a mixture of lithium/borane/THF with basic

hydrogen peroxide;

diminished

yields

of organolithiums

of the phenols

organocuprates.

proceed

in high yield

52811.

Also,

allyl-

halides

Regiospecially with various compounds like

and benzyllithium in excellent generated

1,4-dichloro

[284,285,286].

enolate

of primary halides

of configuration

alkylations

with vinyllithiums

reactions

with

[282]. CCXXVand others

Reaction

have been dialkylated

of methyllithium

of organolithium

new methods of preparing

to give

reagents

unsymmetrical

.

CCCXXXVIL

in

of the organometallic

undergo crossed-Wurtz

systems in the presence

CCCXXXVII [283].

CCCXXXVIII-CCCXLprovides

yield

results

than those of the corresponding

Thus, alkylations with retention

aryllithiums

by oxidation

Two papers have described

[280].

that are more efficient

lithium

cycloalkyl

the use of pre-formed

followed

of

cccxxxv111

with

sulfides

73

cccxxx1x The interaction to afford

metallo

are masked acyl in the following

CCCXL of isocyanides

aldimines carbanions chart.

like

with organ01 ithiums

CCCXLI have been described;

[287]. Related

without a-hydrogens

Some of the chemistry

such compounds

of CCCXLI is shown

compounds have been employed in the

0

R-&D

preparation

of optically

and in the synthesis

of nitriles

CCCXLII, has been prepared a-hydrogens)

with

active

a-amino acids [290].

by reaction

E-butyllithium

of cyclobutanones

Another metalated of the parent Some of

[291-J.

has been described. Li (R~I~P(o)cHNc

CCCXLII

References p_ 95

[288],

isocyanide

isocyanide

(which

the chemistry

of this

12891, system, has

species

74 A route

leading

to the synthesis

cycloalkylidenecycloalkanes boxylic

acids

[ 2921.

Lithium

to

aci-nitroalkylidine

give

also

of

cycloalkanones

esters

like

and lactones

derivatives

salts

or unsymmetrical of cycloalkane

car-.

CCCXLIV has been described

have been reacted

like

in the preparation

been employed

symmetrical

from dilithio

(CCCXLIII)

and substituted salts

of either

CCCXLV [293].

with

nitroenamin

a-Lithioesters

of CT-amide side-chains

have

of cephalosporins

[294-J.

A new preparation has been found

of

vinyl

affords the been for

ketones

provided

investigated; the

reported. give

of

Thus,

the

model

results

R+=C--NHR

of

several

solvent

esters

addition

of

[295].

to give the

carbaniofl

course

aminoketones

of has

seems to be suitable

non-routine like

electrophiles

CCCXLVI 12981,

and lithiodithianes

upon hydrolysis,

afford

with

has been iminocarbon

salts

like

aminoaldehydes

RCH=;RS2

dl

CCCXLVI

sterically

above

The stereochemical

induction

acids

[297].

iminoamines

[299],

which,

with

and B-asymmetric

asymmetric

obtained

give

products

aminodithianes

acylation Two-fold

and carboxylic

used as the

carbinols.

with

carbodiimides of

LIMEis

organolithiums

organolithiums

a variety

CCCXLVII give

several

of

[296].

hindered

no single

prediction

Reaction

ates

in high yields

between

from vinyllithium

undergoes

even more sterically

reaction

ketones

to be successful

2-Lithio-1,6_dimethoxybenzene hindered

CCCXLV

CCCXLIV

CCCXLIII

CCCXLVI I

Ci

[3001

mixed ate complex, ducing agents

since

a,B-unsaturated

they usually

ketones,

A novel ethyl react

LiCuH(n_-C4Hg), and related

CCCL [308].

by Li2CuC14 result

a hydride

for

halides

catalyzed yield

example,

i-propylmagnesium reactions

in

bromide with

of Grignard reagents products

./C02C2H5

in fair

Y----Br

lfil

gem-dibromides

of the halogen

or iodides react with lithium cuprates

by either

l,E-Oivinylbromides

acetylenes

undergo either

metalation

in the synthesis to a,$-unsaturated

alkyl

or copper or both [311].

and 1,2_dibromobenzenes

H20 )

or displacement

mixed organocuprate

of certain carbonyl

with

djs-

An example

with such reagents

C6H5CH=C(CH3)2

and aral kanes, respectively.

A new solubilized

CCCL1

CCCL

’ 3_5(CH3) CuLi C6H5CH=CBr2 ether -80”

afford

catalyzed

[310].

CCCXLIX

is included.

like

of the Grignard reagent

by Li2CuC14 give mixed Wurtz-type

Li+

placement

halides,

esters

with Grignard reagents

homologation

r+H9C=C;u,(C02C2H5

Vinylic

to give unsaturated

gives CCCL1 [309-J. Similar

1,5_dibromopentane

alkyl

[307].

of a,R-dibromoalkanes

yields;

to various

CCCXLIX, has been prepared and shown to

in halopolycarbon

moderate to excellent

to excellent

synthon,

and propargylic

‘Reactions

with tosylates

and aldehydes

acrylate

with allylic

transfer

ones have been shown to be re-

prostaglandins

a,a-Dichloroesters

similarly

depending upon temperature reagent, [313].

[312].

CCCLII, has been found usefi Introduction

compounds may now be accomplished

of ethynyl

group

by the use of

77

cuprate

CCCL111 and subsequent

acetylenes

like

conversion

of

CCCLVby lead tetraacetate

vinylstannanes

[314].

to undergo conjugate

addition

to a,&unsaturated

ketones to give

CCCL111

0

\

vhn(C4Hg)3

J i(CH3)3 C=CH CCCLVI

CCCLV

CCCLIV

Endione CCCLVII has been found to react

with lithium

the saturated carbonyl group at low temperature [316].

anion CCCLVIII from addition ketone

underqoes

ring closure

[317].

This same paper has described

lithium

methylvinylcuprate,

ketones _

Other enolates

phenylselenium

p_ 95

from related

a vinyl

CCCLVIII

at

The regiospecifically same cuprate

only to &-decalone

the preparation

which transfers derived

of this

dimethylcuprate

to an CCCLIX

of the new species, group to a,~-unsaturated

additions

have been trapped

bromide [318].

CCCLVII References

vinylsilanes

Lif

CCCL11

a,&unsaturated

and found

&-C=C-C3H-

(n-C4Hg)3Sn w

enolate

from halo-

been prepared

HwA-cu&J

generated

CCCLIV to

Cuprates derived

for example, CCCLVI, have also

vinyltrimethylsilanes,

like

CCCLIX

by

[3lS].

78

Some other

papers describing

Thus, new additions e-vinyl

sulfoxides

method for involves

of lithium

cuprates

cuprate

[319].

of ate complexes

lithium

of prostaglandins

dimethylcuprate

[321].

mention.

sulfoxides

to give

or B,y-disubstituted

to lactones

complex CCCLXI has been added to cyclopentenone ing synthesis

deserve

A key step in a new synthetic

of 6-monosubstituted

addition

chemistry

to o, 6-acetylenic

have been reported

the preparation

conjugate

lithium

like

butenolide

CCCLX[3’20].

as part of a short

and converg-

Dienone CCCLXII has been treated

as part of a total

synthesis

of 6-vetivone

LiCu ~.<--*5”11)2

0

R

Ate

with

[322].

\\ \ %

CCCLX

CCCLXI

A general with efficient

II

CCCLXlI

ketone synthesis using thioesters and copper ate complexes

utilization

of the latter

has been described

[323].

Pyridine

has been found to undergo addition of various lithium cuprates in the presence of an electrophile pyridine

derivatives

substituted

reactions noids

methyl chloroformate

[324].

epoxycyclopentane

regiospecificity evidence

like

in a total

has been presented of cr-chloroepoxides

followed

by a lithiated

The remaining metals other

Interaction

of lithium

has been successfully synthesis

with lithium epoxide

like CCCLXIII have been prepared

divinylcuprate

with a

employed to achieve [325].

to allylic

dialkylcuprates

correct

Finally,

alcohols

in the

are probably

carbe-

[326].

section

Several

4-substituted-1,4-dihydr

of prostaglandins

that the precursors

papers in this

than copper.

to afford

lithium

deal with lithium

ate complexes

trial kylacetylenicboron

from trialkylboranes

and lithium

of

complexes acetylides.

79

Reaction

of these complexes

or with methanesulfinyl Similar

reaction

CCCLXV13303.

with iodine,

chloride

with propionic Reaction

tetrasubstituted

olefins

gives

acetylenes

acid then basic

peroxide

of CCCLXIII with 1,2-epoxybutane

CCCLXVIwhich can be-converted

chloroacetylide

[329]

then potassium hydroxide,

to hydroxyketones,

depending on co-reagents

CCCLXVIIwith trialkylboranes

like

gives

[331].

gives

CCCLXIV.

affords

homoallylic

[327,328],

olefins

intermediate alcohols,

Interaction

allenes

like

like

or of

CCCLXVIII [332].

/ Li+ R3&CR1

RC-CR’

CCCLXIII

CCCLXIV

1”’ :h==

R2R,

o-)

Li+

\

Interaction

Cz”5 CCCLXVII

of 2-bromo-6-lithiopyridine

new, unprecedented preparation

cleavage

of the pyridine

in high yields

of Z(Z),

L-3333.

Treatment of 9-mesityl-9-boraanthracene

affords

XVII (R=H) which undergoes

reaction

ClO-atom to give XV (R=E) [334].

CCCLXTX References p_ 95

CCCLXV

LiCzCCH2C?

CCCLXVI

specific

RCH=CHR’

with trialkylboranes ring to give

a simple,

affords

a

stereo-

4(E)-alkadienenitriles

(CCCLXIX)

(XV , R=H) with organolithiums with various

electrophiles

at the

80

Convenient have been

routes

realized

to mixed

organoboranes

by interaction

of chloro-

not

available

or methoxydial

by hydroboration kylboranes with

organolithiums [335]. Reaction of boranes with dichloromethyl methyl ether in the presence

of bulky bases like the lithium alkoxide of triethyl carbinol

affords a-chloroborinic esters which are useful in the preparation of internal olefins [336]. Some of the chemistry of lithium triborylmethide (CCCLXX), obtained from the reaction of methyllithium with methanetetraboronicacid (CCCLXXI), has been described [337,338,339]. The prepara'tionof unsymmetrical

ketones

can’be

achieved

by interaction

of chlorodialkylboranes

with

organolithium adducts of t-butylisonitrile [340].

While gem-dialuminum species CCCLXXII has failed to give olefins with ketones, prior treatment with c-butyllithium apparently has given CCCLXXIII which part

acts

as a methylenation

agent

towards

of a study of the stereochemical

aldehydes

and ketones

C3411.

course of cleavage reactions, inter-

action of aluminum compound CCCLXXIV with methyllithium affords an intermediate ate.complex that undergoes reversible dissociation to a carbanion that undergoes inversion [342].

CH2(AlBr2) 2

LiCH2A1Br2

2

CCCLXXII

cccLxx111

As

CCCLXXIV

81

The mechanism and stereochemistry For example,

been studied [343].

4-t-butylcyclohexanone

occurs

In contrast,

alcohol.

A similar

are cited. aluminate

to give alcohols of berylium VIII.

of certain

have been reported

Lithiation

acids.

At -75”,

benzoylbenzoic selective lithium give

at -loo”,

benzoylbenzoic

cyclizes

has been prepared

Also,

bromobenzoic

salts

react

The isomeric

exchange rather

As above,

various

acids

a :I

Li

CCCLXXV

References

p. 95

tetramethyl-

alkoxide

to give

dilithio

of temperature

L-3471.

esters.

at -Zoo to give

with esters

complexes

give

the lithiated

to benzocyclopropene by treatment

CB” CH3

r

CCCLXXV I

Though such

likewise

undergo

with n-butylat -75”

to

undergoes metal-halogen

CCCLXXVII[349].

1

like

substituted

to the ester

ether which,

of iodoferrocylmercury

=

to afford

undergo self-condensation

Bromoether CCCLXXVIalso

salts

benzoylbenzoic

methyl bromobenzoates

[350-J.

COBLi

Other examples

of lithium

than addition

these species

exchange a+ -QO” to apparently one hour,

[345].

they self-condense

[348].

metal-halogen at -95”.

magnesium, and zinc

ate complexes of selenium with ketones

as a function

these dilithio acids

to give equitorial

Exchange Reactions

CCCLXXVhave been re-examined are stable

to

[346].

of the isomeric

species

attack

alcohol.

additions

has

tetraalkylaluminates

of boron, axial

to ketones

[344].

has been described

Lithium-Halogen

by axial

to afford

study of conjugate

the reaction

of lithium

ate complexes

attack

has been published

Finally,

addition

predominately

related

occur mostly by equitorial

of ate complex addition

upon heating

for

1,2-Dilithioferrocene

with excess

n-butyllithium

82

A variety

of vinyl

of t-butyllithium like

in THF [351].

dimethyldisulfide

ketones

bromides have been converted

to afford

Such species

have been reacted

a simple alternative

route

by.means

with electrophi

to ring enlarged

as illustrated.

_ SCH3

CH3SSCH3

a-Lithiated like

to vinyllithiums

lithiocinnamates

CCCLXXIX[353]

and fi-butyllithium aldehydes

CH3C02H

(CCCLXXVIII) [352]

and a-lithiated

have been prepared from the corresponding at low temperatures.

represents

another

Condensation

acetals

bromo compounds

of the latter

with

example of directed_ aldol izations.

,C02Li CH2=F-CH(OC2H5)2

C6H5CH=C\ Ll

Li CCCLXXIX

CCCLXXV III

A new preparation like

CCCLXXXI

sumably occurs

of 3-butylalk-1-ynes

and E-butyllithium via dilithio

salt

(CCCLXXX) from 1-bromoacetylenes

has been described

[354].

The reaction

pre-

CCCLXXXII. Li

R HECH

RCHC-CLi

RCH2C=CBr

F “-C4Hg

CCCLXXXI

CCCLXXX

The preparation system, cccLxxxIv

of the first

known derivative

CCCLXXXIII, has been prepared by reaction c3551.

9,10-Dihalotriptycenes

CCCLXXXI I

of the acepentylendiide of n-butyllithium

have been reacted

with

with a variety

of

83. basic reagents in an attempt to form bridged triptycene CCCLXXXV [356].

However, though single reaction desired

metal-halogen

with electrophiles,

exchange was realized

the bridge

could

as evidenced

not be closed

to give

by

the

product _

Cl

cccLxxxIv

CCCLXXXV

Finally,

two papers have described

CCCLXXXVIto lithioselenides [345,3571.

like

the conversion

of gem-diselenides

CCCLXXXVIIby means of E-butyllithium

The latter compounds are masked vinyllithium reagents.

R,

,SeC6H5

'YLi R' cCcLxxxv1

References

p. 95

like

84

IX.

Reductions Reactions

and Radical

Anions

of the radical

anions and dianions

13581,and the base-catalyzed [359]

carbon-carbon

of aromatic

addition

hydrocarbons

reactions

hydrocarbons

of

have been reviewed_ Reductive

described strained

cleavages

of cyclopropyl

which provide tricyclic

a convenient

a7coho’is

[360].

rings route

to otherwise

The process

sion of CCCLXXXVIII to CCCLXXXIXin a yield

reduction

gives

mostly

of benzocyclopropane

2,5_dihydrotoluene

in ammonia have been difficultly

is illustrated

of 90%.

though slow at -33O, afford

vinylcyclopropane, Also,

by lithium

Similar

accessible

by the converreductions

mostly Z-E-pentene

(CCCLXXVII)

of

at 25” [361].

by lithium/ammonia/ethanol

t349-j.

5

CCCLXXXIX

CCCLXXXVIII In connection

with prostaglandin

pentene derivatives

&-CCCXCI

chemistry

diketone

[363],

above refers

cccxc

unsaturated

have been reduced by lithium/ammonia/alcohol.

and the corresponding affords

syntheses , several

give cis-

and trans-CCCXCI [362],

and CCCXCIII gives

to the alkyl

CCCXCI

trans-CCCXCI 13641.

side-chains

cyclo-

Thus CCCXC CCCXCII The stereo-

only.

CCCXCII

CCCXCIII

85 Lithium/ammonia reduction

of quinoline

has now been shown to afford

1,4-di hydroquinol ine (CCCXCIV) , not the previously ‘isomer dihydro

The Birch reduction

[365]. product

be obtained

of N-methylindole

CCCXCVin high yield

by distillation

reported

1366).

1 ,2-di

hydro

has been shown to give

The conjugated

of CCCXCVfrom an acidic

diene

ion-exchange

CCCXCVIcan resin.

mI’

:I (x;s

I

I

H

I

CH3

Lithium reductions

of biphenyl

and certain

examined in ammonia in the absence or presence arnnonia and the extent phenyl has also lithium

of reduction

been effected

derivatives

of certain

steroid

of a proton

source

Similar

Tetralin

as a model for

References

p_ 95

reduction

to afford

than of bi-

di-

and

Z-Methoxytetralin related

[370].

&i(CH ) 33

CCCXCVI I

other

has been reduced by

CCCXCVIIand CCCXCVIII 13691.

derivatives

have been

derivatives

of chlorotrimethylsilane

has been reduced by lithium/HMPA/ethanol ductions

of its

compared [367].

in HMPA[368].

in THF in the presence

tetrasiiylated

CCCXCVI

cccxcv

CCCXCIV

cccxcv111

planned

re-

86

A systematic benzenes

study of the alkali

under aprotic

affords

only diol

conditions

has been described

CCCXCIX-ketoalcohol

gives

CD with lithium/ammonia

tions

of the meta isomer are sluggish.

observed

metal reductions

of the isomeric [371].

The para isomer

The ortho

is absent.

isomer interestingly

and CD1 with potassium/ammonia. Explanations

dibenzoy

Related

reduc-

are given to justify

the

products_

,,,,q=J!a,“,

Several

other

alcohol

which,

ketones

fair

formations

cr,f3-unsaturated [374].

non-epimerizing derivative

by lithium

esters

is converted

C-silylation

CDVI [375].

by lithium/ammonia/alcohol

CD11

Finally,

of chlorotrimethyl-

ketone has been converted

have been shownto

the conversion

to diketone

of ~1. B-unsaturated

of benzoate

to constitute

transa

CDV to methylene

the scope of the cleavage

has been determined

to CDIV in

undergo similar

Lithium/ammonia has been demonstrated method for

been reduced by

in ammonia/t-butyl

in THF in the presence

Thus, methyl a-methyl vinyl

[373].

to a diol

by chromium trioxide,

example of direct

has been effected

yield.

compounds have also

CD11 is converted

upon oxidation The first

CD111 [372].

silane

carbonyl-containing

Thus, 1,4-diketone

1ithium.

CD1

CD

CCCXCIX

of benzyl esters

[376].

CD111

Known cleavages have been applied Similar

CDVI

CDV

CDIV

of ally1

alcohols

to the syntheses

reductions

and ethers

by 1 ithiumjanznonia or amines

of vitamin D3 [377]

of tetrahydrocannabinols

[379]

and desmosterol

and of certain

[378].

epoxides

[380]

have been reported. An interesting curation

of olefins

by lithium

amine synthesis

has been described

which involves

to give species

like

Reduction

in THF completes

CDVIII, suitable

for

the process.

stereoselective

CDVII [381]. A new

reduction

crystalline

of ketones,

aminomer-

of the latter

reducing

agent,

has been described

[382-j.

I I

RNH-C--CdgBr \

1

CDVIII

CDVII Turning to radical-anions, lithionitroalkanes, the sulfone

lithioesters,

group [383].

o-nitrosulfones and other

The reaction

have been found to react nucleophi les with displacement

which proceeds

in high

illustrated.

f

References p. 95

(CH3)2::02

DMSO,

H2°)

yields

is

with of

88 Aliphatic

to undergo

and

cleavage

trimethylamine step

convert with

of

like

certain

the

lithium

a-amino at

acids

have been found

of naphthalene

adducts

Finally,

this

radical-anion

to their

dilithio

salts

the a-carbon

CDIX

to afford effects

like

CDX to

a one-

give

has been employed to which

undergo

reaction

[3g6].

I-

Reactions

with

Inorganic

conversion

a-hydroxyesters

dine-HMPA

CDXI

CDX

A novel to

like

same radical-anion

Diels-Alder

COIX

X.

This

RH [384].

[385].

iodides

radical-anion

benzyne-furan

CDXI

electrophiles

R&(CH ) 33

with

trimethylammonium

and R-R and/or

aromatization

naphthalenes

aromatic

and

of

has

Organometallic

ketone

enolates

been effected

acyloins

and

of

ester

enolates

by a complex of molybdenum peroxide-pyri-

The process

(MoOPH) [387].

to

Compounds

is

illustrated

by the conversion

of CDXII

to CDXIII_

0 LiN(i-C3H7J2

‘bH5

CDXIII

CDXII

Treatment phosphine

of palladium

constitutes

in high yields; yield

bH5

H2°,

MoOPH -70” ’ 1 hr.

‘,

THF

for

of 95% [388].

complex

a convenient example,

CDXIV with

method of preparing

methyllithium

A gold-containing

organolithiums

and triphenyl-

c-alkylbenzaldehydes

and CDXIV give @olualdehyde

compound, CDXV, somewhat similar

in a to

s9

CDXIV, has been prepared by treatment gold

(I)

bromide-triphenylphosphine [389].

CDXVis thermally

and is useful

in the preparation

plexes

of g-lithiobenzyldimethylamine

or with alkylgold-triphenylphosphine stable,

exists

as a discrete

carbene

illustrates

carbene

are

Treatment of CDXVI with n-butyllithium-TMEDA

apparently

affords

like

the latter

References p_ 95

ligands

by deuteration.

CDXVII

known, with c-butyllithium

weighed in air

metal-

u-hydrogen

Treatment of chromium species

chloride;

of transition

containing

anion CDXVIII as evidenced

electrophiles

chemistry

of CDXVI from CDXVII and neopentyllithium

carbenoid

CDXVI

acids

additional

The preparation

that nonstabilized

stab1 e [390].

dimer in benzene,

CDXV

papers have described

complexes.

com-

of uncomplexed (RAu)n species.

CDXIV

Several

with

epoxides,

[391,392-j.

CDXIX, one of the most acidic at -78O gives

a-bromoesters,

electrophile

CDXVIII

affords

neutral

carbon

CDXXwhich has been reacted

with

and bis(triphenylphosphine)iminium a stable

An attempt to prepare

salt

of CDXXwhich can be

a vinylphenylcarbene

complex

90

from CDXXI and vinyllithium

gave 1-phenyl-1-methoxy-2-propene

in a yield

of 434

[ 3931.

CDXXI

CDXX

CDXIX

More examples of group IV elements o-bonded to be described.

Thus, treatment of molybdenum

in ether

affords

CDXXII in a yield

products

are thermally

1,4_dilithiobutane -30" [395].

open-chain

stable

gives

and chemistry

a-Alkyl

dichloride

of CDXXIII is contrasted

The with

with that of

and a-aryl of methyl-

containing

_M

cp2T’A/YY CDXXIV

CDXXIII

titanium

derivatives

like

and perfluorophenyllithium Similar

with organolithiums

dichloride

[394].

CDXXIII, which is stable below

0

tanium at -35O [396].

sulfur

of titanocene

Cp2T-

CDXXII

chloride

is similar

CDXXIV.

Li4Mo2(CH ) 38

interaction

Reaction

at 25”.

metals continue

(II) acetate with methyllithium

of 81%; vinyllithium

the new metallocycle,

The stability

to transition

titanium

treatment has afforded

CDXXVhave been prepared with chlorotriisopropoxyti-

of monoalkyl-

or aryltitanocene

mixed complexes

like

CDXXVI. The

compound COXXVII has been prepared from titanocene

and li thiomethyl thiophenol

[397].

RTi (0-i_-C3H7)3

CDXXV

by

CDXXV I

CDXXVI I

91 Mixed obtained (M=Rh,

a,n-type

from Ir);

in

obtained

of rhodium

and

iridium(CDXXVII1)

1,4-dilithio-1,2,3,4-tetraphenyl-1,3-butadiene

a similar

In contrast, sulted

compounds

reaction

interaction

displacement

on CDXXIX

of dilithio of

only

one

salt chlorine

have and

been

CDXXIX

(M=Co)

gave

a sandwich

compound

CDXXX

with

titanocene

dichloride

atom

and

a cyclic

compound

13981. re-

was

not

[399].

IAM\,

I

653

I

CDXXIX

CDXXVIII

?z

cl-N

1

I

Cl

c1

\

Li

/

Li

I

Cl

’

Cl

CDXXX

The has give

been

described

CDXXXII.

retained give

preparation

in

reactions like

For

[400].

Silicon-,

compounds

References p. 95

of transition

of

metal

example,

germanium-,

compounds CDXXXI

and

perfluorophenyllithium

CDXXXIV

[401].

containing

and

tin-iron

polysilyl

bromomanganese and

with

manganese compounds

ligands

pentacarbonyl bonds like

have

CDXXXIII

been to

92

c(CH3)3Si)2

Si\/CH3

((CH3)3Si)

2 kn(CO~S

Li CDXXXI

CDXXXII

(C6F5)3GeFe(C0)2Cp

Fe(C0)2CpGeC13

CDXXXIV

CDXXXIII

The first monomeric metallocenophanes bridge have

been

described

by

the

process

with a heteroatom comprising the shown where

M=silicon

and

germanium

[402-j.

TiC14

2E-C4HgLi THF

Cleavage sis,

silylmercury

sifacyclopentane

intramolecular cyclic

of

addition

methylcyclopentane

compound

CDXXXVI

14031.

of

to

Si-Li

A related

organosilanes.

dianion

Z+

CDXXXV with The

an olefin

cyclization

lithium

reaction and from

is

gives, the

constitutes mercurial

after

first

example

a new route CDXXXVII

affords

[404].

CH2=CH(CH2)3Si

(CH3)

2f

Hg

“3

2

CDXXXVI

CDXXXV

“g

CDXXXVII

hydrolyof to

an

93

A rare example of a compound (CDXXXVIII) containing has been synthesized triphenylstannane

of p-chloromethylthiocresol with lithium The corresponding germanium compound was prepared

[405].

Mono-, di-,

by reaction

of gallium

[406] _

alpha to tin

by treatment

similarly.

reagent

sulfur

or trialkylgallium trichloride

For example,

compounds may now be synthesized

with the appropriate

tri-E-butylgallium

amount of organolithium

has been obtained

in a yield

of

97%. C”3

( C6H5)3SnCH2S’ CDXXXVIII Additional treatment

carbon-phosphorus

of lithioethyl

C0XXX1X L-4071. affords gives

isobutyrate

Reaction

COXL [408].

systems have also with diethyl

of dilithioethylphosphine

Addition

to give

phosphinomethylphosphine

sulfides

[SlO].

with sulfuryl

References

p. 95

sulfide

s

(C6H5)2P-CH2Li

CDXL

afford

cyclopentadienide

CDXLII; such molecules

of lithium

chloride

CDXLI

with arsenic

diphenylarsine

has been shown to give only tetraphenyldiarsine reacted

chloride

-C2H5

of lithium

Interaction

ester

chlorodialkylphosphines

0

CDXXXIX

thereof

gives

[409].

C02C2H5

derivatives

For example,

to triphenylphosphine

by various

/P(O) (OC2”5)2 (c”3)2C\

Reaction

chlorophosphate with g-phthaloyl

of methyllithium

CDXLI which has been phosphorylated

been described.

trihalides

have fluxional

with aromatic [4111.

to give alkanesulfonyl

or methyl structures

ketones and quinones

Organolithiums chlorides

in fair

have been yields

94

[412]. A new, improved preparation of tris(dialkylamino)boranes(CDXLIII) which involves reaction of lithium dialkylamides with boron trifluoride etherat has been described

[413].

A similar reaction between chlorodiethylaluminum'with

a substituted lithium piperidide affords CDXLIV, a compound that effects regiospecific

isomerization

of epoxides

to allylic

alcohols

[414].

(R2N13B CDXLII

Several

CDXLIV

CDXLIII

new ring systems containing

silicon

and nitrogen

have been prepared

from appropriate lithiated diamines or hydrazines and dichlorodisilanesor siloxanes. The systems include CDXLV [415], CDXLVI [415], and CDXLVTI [416]; the substituents on each ring are methyl groups.

CDXLV

CDXLVl

CDXLVII

Bis(trimethylsilyl)diiminehas been converted to 1,2-dianion CDXLVIII in ether but only to the corresponding radical anion in TtlF[417-j. The latter compound is thermally unstable and its mode of decomposition depends upon the metallic cation, the temperature, and the solvent. Reaction of lithium bis(trimethy?silyl)amidewith tin (II). . chloride gives the novel amino derivative

organosilyl-

CDXLIX in which the tin is stabilized as Sn (II) [418].

95 Li ((CH3)3Si);-Sri---

(CH3)3SiNy;i(CH3)3

CDXLIX

CDXLVIII

Interaction gives

CDL

CDL1

[419].

sequence

of

which,

(Si(CH3)3)2

lithiohexamethyldisilazane

upon

A related

affords

distillation, compound,

with

CDLII,

trichloride

phosphorus

acid

the metaphosphoric

has been prepare’d

derivative

in a similar

reaction

[4201.

((CH3j3Si)d/Cl r-

J CDL1

CDL

t-C4Hg 1.

N-P=N-+-C4Hg

(CH3)3Si'

CDL11

Finally, pared

from

the

certain reaction

silylated

like

CDL111

of lithiodimethylphosphine,

The acid-base

halosilane

[421].

phosphines

has been discussed

H3SiP(CH3)

phosphines

chemistry

of

and

aluminum

such

species

CDLIV

have

been

chloride,

and

with

lithiated

[422].

(CH3)3SiP(CH3)2

2

CDLIV

CDL111

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