Lithium annual survey covering the year 1971

1

LITHIUM ANNUAL

SURVEY

WILLIAM

COVERING

THE

YEAR

1971

H. GLAZE

Department of Chemistry, Denton, Texas 76203

North

Texas

State

University,

CONTENTS I.

Structure

II.

and

Kinetics

Studies

1 7

and Mechanisms

Lithium

III.

Bonding

Carbenoids

and Other

Halogen-Substituted

Organo13

lithiums Lithiations

IV. V. VI.

Polymerization

Reactions

Reactions

Heterocyclic

Addition

VII.

(Hydrogen-Lithium

with

Reactions

Exchange

Reactions)

22 28 29

Compounds

to Carbonyls,

Olefins,

and

Similar

Substrates Miscellaneous

VIII.

Reactions

IX.

34 Organic

with

Reactions

Inorganic

41

and Organometallic

Compounds

45

References

I.

52

Structure Further

appeared. data

and

evrdence Bywater

on several

charge

Bonding

Referencesp.52

on the nature

and Worsfold

compounds

on the phenyl

for benzyllithium

Studies

ring

in c6D3

of benzylic

lithiums

Cl1 have presented

of this

type

is estimated and THF-d9

has

UV and PMR

in benzene

and THF.

to be 0.29

e and

respectively,

and

0.53

The e

is found

W_EiGLAZli

2

to

increase

Styryl ionic

increasing

with

and a-methylstyryl

McKeever

atoms

lithium

little

have very

are said to be largely

excess

degree

however.

densities

the same method

is the observation (as measured indicating spectrum lithium

that the total

Ring charge

authors

was observed

ring positions

charge

is a minimum

some type of specific

C&l.

solvents.' to indi-

at the a-carbon

in THP/C6H6

in the two previous

by PMR shifts)

position

in TH.l?as

and Yuki have reported

(DPB-1

of a-picolyllithium

indicating

coupling

Okamoto

at the various used

by these

complex

that the carbon-lithium

mixtures

PMR data 131.

were measured

papers. density

Very

by

striking

on the ring

at CTHF]/[DPB-I formation.

(I) is similar

is somewhat

the-

and benzyl-

in non-polar

of sp3 character

on l,l-diphenylbutyllithium Charge

charge

interpreted

C2, AS 63; 11.. No 13C-'Li as -lOOOC,

their

ionic Cn.

solvents.

in l,l-diphenylhexyllithium

and 13C data have been

cate a substantial

low

compounds

on the side-chain;

and Waack have reiterated

that the a-carbon

atom

substitution

in -character in both polar and non-polar

other hand,

It:

alkyl

..

= 2 .'

The PMR

to that of benzyl-

greater

in I, however,.

bond may be more

ionic than

in benzyllithium. Electronic

spectra

fluorenyllithium

of l,l-diphenylhexyllithium

are markedly

CH30CH2CH20Li

[51.

disappearance

of the contact

"coordination-agent cx = CH30,


With

effected

by the addition

fluorenyllithium,

separated proposed

and 9-

the agents

of cause

ion pair and the formation complex"

RLi

l

: the

0f.a

2XCH$H2CH20Li-

to have the following

structure:':

, 3

LITHLUM

The

spectrum

preted

of fluorenyllithium

in terms

Further species

of separated

information

has been

ion pairs

ion pair

this

past

published

more

has

fcrmation

on the structure

published

c7, AS 70; 2561 have

in ethylamine

been

C6l,

of allylic Burley

year.

information

inter-

lithium

and

Young

pertaining

to

of II:

PQ@yPh LP

Me

II

PMR data

on "living"

Dolinskaya that

only

vents.

et al. --

butadienyllithium

C83 and by Morton

the primary

However,

form

in basic

III

has 193.

Both

is present

solvents

the

been

reported authors

by conclude

in hydrocarbon

secondary

form

sol-

IV may

/CH=CHz -CH*-CH=CH-CH2Li

-

CH25H Li

IV

III

-CH

2,

C /.-‘A c--a

‘C

Li@

-

IV

Cfi&

s

.

-CH2

V

exist the

Sinn and of dienes

ionic

in all cases,

the

increase

isoprene

p. 52

been

used

proposed

as these

trans-1,4

isomerization

that

of

and 1,2

As proof,

of initiator the

cis-1,4

in-chain-units

in polybutadiene

to study

the addition

is exclusively

processes.

content

as the concentration

PMR has also References

such

isomerization

in cis-1,4

- trans

V and VI.

cl03 have

species

and that

from bimolecular

in the cis --

forms

coworkers

to form

LiQ VI

as an intermediate

(largely)

I

reaction

result

they

cite

and poly-

is decreased. products

of iso-

W&-CL&

4

prene

and. l-l-diphenylbutyllithium

cis-4,l

addition

products,

[AS 70; 2563.. Addition of these

products,

isoprene

and DPBLi.

dienyllithiums dissociation


but no trans

of THF causes

forms, were

:-

found'...... -:._ ..

not only the isomerization

but also the reversal In another

-and,::

e-1,4

C113.

report

of the reaction

conductivities

in THF have been used to calculate

to--~:. .--

of polyp_- ..

constants.for

into free ions C121.

Indolyllithium solvent-separatea VII undergoes

VII was reported ion pairs

rapid

in THF

exchange

with

to exist primarily

t13l. indole

PMR spectra above

as

show that

-3OOC.

VII

Ring proton

shifts

give no indication species

for VIII

of the participation

Me

fi--Cl-l&

de

Lithium-7 dienyllithium, reported

THF,

~157.

solvents distance

and.HMPA.

reported

and

of homoconjugated

Me

‘:C' 1: i 'CH2

IX

VIII

anion

of pyridines

such as IX Cl43.

Me

ferent

are typical

nmr spectra

of fluorenyllithium,

indenyllithium, Variations

and phenylallyllithium

in the 7Li chemical

are interpreted as the solvent .Lithium-7

cyclopenta-

in terms changes

shifts

shifts

of increasing

have been in dif-: cation&

in the series EtpO,

of thirteen

dfanions

DME;.

also-were: :

ClSI.

. PM,P,.UV, .and IR for cyclopentadienyllithium

...:

indicate

-.:.’

%hdt.l:

5

LIniIml

the compound

has a delocalized,

Fluorine-19

and

proton

cyclopentadienyl However,

anions

a considerable

substituent

CsH4_

Lithium-7 tolyllithium preted

spectra

in Et20

in terms

species

*LiPh

t

association

view,

o_C the

of mixtures

LiPh

of PhLi

+

in general

negative

is present

C171.

Cl83.

charge

of the

in its CT orbitals.

of phenyllithium

temperatures process

ebulliometrically

Z

LiTol

portion

at reduced

structure


this

of an exchange The

(191.

for

confirm

probably

spectra

not a diene-type

have

involving determined

and pbeen

only

intermonomeric

degree

cf

*LiTol

(i = 21, reported

earlier,

was

concluded

to

be in error. Infrared been

spectra

interpreted

to the case

of n-butyllithium

in terms

in non-donor

of decreased solvents

complexes

of n-BuLi

hexamers

have

been

determined

[21l.

were

also reported.

data

A vibrational

analysis

has confirmed

the

Li-Li

bonding

based

on 7Li spectra

butyllithium Vapor lithium

has

type

been

has been

Referencesp.52

of t-BuLi

based

hexameric

indicate

over

from

as compared constants

diethyl

for

ether

on IR and Raman structure

with

c22l.

previous

PMR spectrum

No

findings

of s-

1231.

of benzene

solutions

that

the range

information

obtained

The

have

n-Cl2H25Litetramers

tetrameric

in agreement

lowering

bonding

with

with

reported

ethers

Stability

Complexes

proposed

and n-octyllithium

Some further

C201.

[AS 68; 1891.

also

C-Li

and tetramers

indicated,

pressure

predominantly

t243.

was

in several

both

of n-pentyl-

compounds

of concentrations

regarding

aggregates

'Li spin-lattice

are studied

of this

relaxation

times

.-.

6

1253.

W_H;GLAZE Temperature

dependence

of

T1

for several

organolith~%ums~~: .-

indicate tion-

that

rates

symmetry

tetrameric

than

do

species

hexamers,

appeared vious

reports

The results

structure

some unusual

contains

greater._'.'.-. j

in the magni;

O°C was attributed

for MeLi and

are in general

two Li-C-B

of LiB(CH914

features bridges,

agreement

with pre-

of interest

has been reported 1273.

The

the first reported,

\._n:

and

compound

one of which

C(3)

f+&_

to

(MeLi)& have also

[AS 69; 21.

The crystal shows

the

,.

&l&a-

of the aggregate.

Hiickel calculations

[261.

to

change

in Et20 near

change

quadrupolar

due

An unexpected

tude of Tl for methyllithium

Extended

slower

presumably

of the tetramers.

some type of structural

have

75.6’ C(2)

Fig.l.Molecularstructure ofLiiCH3)4.AlloftheatomsexceptC(l)andC(l)'lie ina

crystallographicmirrorp~newhichhasitsnormalperpendiculartotheplane ofthepaper. C(1)isre!ated to C( 1) ‘by the mirror plane.

7

LITHIUM

is bent

(Li-C(l)-B

(Li-C(Z)-B short

angle

angle

75.6O) The

179.6O).

in the nearly

the

linear

other

B-C and

bridge

nearly

Li-C

linear

distances

are

suggesting.a

bond,

very

strong

link-

age. Kinetics

II.

and Mechanisms

Reviews

have

and mechanisms acids

[30],

anions

and alkyl

chemistry

tration RLi.

data

reactivities

has

microstructure composite plain

the observed

rates

of polymerization

butyllithium rapid

the

variations.

and menthyllithium.

initiator

[-AS 69;81

propagation

of isoprene

be

first

and

The accelerating reported

C40].

References p.52

0.25

used

respectively

with

respect

latter

[37].

of 2,3_dimethoxybutane

relative by s-

is an extremely period

in

of the rate has been

in cyclohexane has

also

The

to ex-

initiated

induction

studies

to

on the

by the author

styrene

69; 4].

concen-

[38] has measured

and

Kinetic

with

polybutadiene

Selman

The

order

by polyisoprenyllithium

order

effect

[9] was

vary

re-

C36, AS

of temperature

and the usual

is not observed.

nuclear

dynamic

appeared

reagents

effect

of isoprene

cyclohexane

to

lithium

of Morton

as intermediates

of organolithium

has

of alkyllithium-initiated

mechanism

radical

to organolithium

in the kinetic

discussed

of

paper.

in Et20

of the

acidities

involving

induced

on the addition

due to differences

Uraneck

anions

Some reference

to l,l-diphenylethylene

Relative

reactions

radical

in each

the kinetics

C28,29],

and chemically

1321,

kinetic

concerning

transfer

[31],

r-33,34,351.

Further agents

halides

is contained

year

polymerizations

electron

chemistry

polarization

this

of anionic

carbon

in organic

appeared

of shown

1391. been

Pree radical

chain

processes

have been

the reactions

of 2-lithio-2-nitropropane.with

pane and with

2,2_dinitropropane

Several

similar

has reported

systems

were

the reaction

The radicals

carbanions, which %. Lewis bases.

also

BuLi

are converted

-

to their

are accelerated

Bu-

Screttas

the stable

'-diyl)-2-phenylallyl

processes

of light-i?+13.:

investigated. with

+

I;::.

2-bromo-2-nitropro:

in the presence

of n-BuLi

cals 1,3-bis(biphenyl-2,2 methyl,

demonstrated~for

C423..

free radi-

X and triphenylcorresponding-

by the presence.of

I_#+.

x

The kinetics nitrile

in Et20

is 0.67 order

rate constants showed

of the addition

for several

a very low effect

irregular).

A concerted

of phenyllithium

in PhLi

C433.

A Hammett

m- and p-substituted

of polar

substituents

electrophilic

to benzoplot of

phenyllithiums (p = -0.035;

substitution

mechanism

of the type shown below was postulated:

PhLi

c

PhCEN

. .

:.

Batalov

and coworkers

continue

to report

their

finding

on

--

_ ‘-1 the

exchange

reaction

between

phenyllithium

and bromobenzene.

[AS 70; 2643.

Tetraalkylammoniwn

halides

accelerate

change

C443 while

halides

depress

_.

the ex:;-

process

c45,461.

An electron

lithium

donating

group

the rate- .’ .:-

(p-Me) in the aryllithiw

‘_.

:

LITHIuhf

was

9

shown

to increase

decreased used

the rate

state

rate

Substituted

1473.

to investigate

transition

exchange

the

polar

for the

p-Cl

substitution

bromobenzenes

and a polar

effects, exchange

while

process

were

four

has been

also

center postulated

1481. The reaction in BuLi

and 2.5 order

No particular noted,

reactions

which

by n-BuLi

1501.

alkyllithium pretation

that

interesting

Multiple

in hexane

is first

to a recent however.

have

pointed

report

out

c493. be

secondary

of THF and Et20

of ethylene

undoubtedly

order

It should

the decomposition

additicn

yields

complicates

higher the

inter-

results. of 1,3-dithianes

stereochemistry

(slow)

workers

which

derivatives

by reaction

THF

proposed,

during

compounds

Lithium

followed

was

other

occur

of kinetic

with

in THF according

mechanism

however,

of XIII

of n-Buti

with

yields

the

[513

.

produced

Lithiation

DC1 yields same

have

only

of XI whereas

XII,

some

(fast), lithiation

product.

Me

Lithiation

of XIV

equatorially

XIV

followed

deuterated

by reaction

product

with

XV, while

xv

the

t99%)

MssqD::: ;“c:i- Ms>H XVI References

p_52

XVII

(99.5%)

DC1

yields

lithium

only

the

derivative

w&

10 .of XVI

yields

only

the

equitorially

protonated

:

$$+&-. -:,.I..-.:

XV~~.~:i._;~z_~~.‘:

product

-__.:

Thus, are

lithiation

highly A

of

RLi

and

of

these

processes

[cf.

organosilanes

has

compounds

in which

c543.

Further

y

the

Ptl

n-BuLi

on

= a-naphthyl) 70;

the

been

with

.,-_.z__ : .~

3871.

the

intermediate

._

occurrence

of

subject

of

XIX

indicated

was

so&e

1,6-hydrogen

.-

N-&H-Ph I

II H.,Q “C-N

‘Ph

Ph’

in pentadienyl

2641.

Metalation

of

anions linolenyl

cyclize and

has

on XXII,

also

alcohol

standing. which

are

been

reported

gives

t55,

AS

70;

heptatrienyllithium

Rearrangements forbidden

by

such

as

orbital

+

.

xx

XXI

_

by-the _‘.

Li

Fh\

4

that of XX to XXI

prepared

:

have

bridging

Ph’

shifts

which

been

85 belowJ-.]

R-ii---H

[53]

Ph

compounds

AS

reference

Naph

information

‘N-CH2-Ph

[52,

c

rearrahgements

work

Naph

derivat-ivesI,'-; 1-1 ,_:y_. ..' y-I-.

lithium

Ph

(R=Me,Et,n-8u. t-Bu.neo-Pent?

recent

Li@

= menthyl;

RLi

Anionic

Ph’

(Men

RMgX

Fh I MenO-Si--H I Naph

Ph

chiral

of XVIII

various

protonation

stereoselective

series

reaetion

and

XXII :-

11

LITHIUM correlation

rules,

the participation process

of the

to be allowed.

linoleic the

nevertheless

acid

was

in 1,6-sigmatropic been

searched

lithium

The

may

group

authors

cause

CS63.

allylic

Long

the allylic

Cl,41

lithium

.,g--

Ph’

Pkf$bLiO

THF or TMEDA

2

Ph

,c

D2 k

analysis

of XXIV

scrambling

which

would

Similarly,

no [l-43-carbon

showed

be required shift

1,3-Cycloaddition been

reported

CD2

XXIV

Li@

no evidence

for deuterium

by a [1,43-hydrogen was observed

from

shift.

XXV.

Me

PI-I -

reactions

to occur

of Z-azaallyllithium

in moderate R”

References p. 52

cs71.

QD D

H

n -6uLi

have

XXIII

Ph’

Ph

and/or

resulted

shifts

compound

Ph p

However,

also

/TPh

XXIII

of

position

exposure

Sigmatropic

that

the migration

,CDz BuLi

feel

of the monomethylamide

at the doublic

migrations.

for using

atom

Lithiation

observed

site a to the amide

do occur.

to high

yields

to dienes 1581.

have

I2

.- Asymmetric complexed

synthesis

with

For example,

by means

(-)-sparteine

reaction

alcohol

XXVII

with

benzene

followed

of

alkyllithiums

XXVI has been reported

of n-BuLi

6% optical

- XXVI with benzaldehyde

purity,

by carbonation

while

lithiation

gave XXVIII

with

yields of ethyl

30% optical

purity.

?”

(1)PhCHO t2)~'

n-BuLi/XXVt

Ph-7-H Bu XXVII

(1)

PhCH2CH3 (2) COz;H+ I CFi Ph-&-t-l &,H XXVIII

More details chlorides

have

optically

active

on

the

reaction

of

phenyllithium

c60,61, AS 70; 2871.

appeared

3-chloro-cis-1-butene-l-d

PhLi Etgd

XXIX

H

xxx

with

allylk

y-Coupling

yields

two

with

products

Me

Me (RI-(-)

XXIX syn

D Ph (minor)

and XXX with attack

optical

as shown

purities

in XXXI.

indicative

of a stereospecific

LITHIUM

13

The mechanism triarylsulfonium radicaloid,

of the reaction salts

and

direct

cesses

are rejected

furane

intermediate.

III.

Lithium

has

been

of organolithium

discussed

nucleophilic

in favor

Carbenoids

by Trost

aromatic

of a mechanism

and Other --

reagents c621.

Benzyne,

substitution involving

with

pro-

a sul-

Halogen-Substituted

Organo-

lithiums Metal the

carbenoids,

subject

has been

of a recent

used

derivatives prepared

review

those C631.

for the preparation

fluoroethyllithium ethyllithium

including

CSSI.

The

latter with

in situ, _-

react

solvent

been

system

THF/Me20

and l,l-dichloro-2-X-2,2-(ethylenedioxy)-

of the

epoxides,

The

have

of l,l-dichloro-2,2,2-tri-

CX = Ph, H, and Mel

yield

of lithium,

are described.

carbonyl

whereas yields

[6L1,65, AS

compounds

a,&unsaturated with

LiCH2Cl

have

described

69; 183.

Reactions

of LiCH2Br,

have

shown

been

carbonyl are

Various

somewhat

to

compounds

do not

lower.

,Br C”2,

Schlosser

er

and coworkers

cyclopropanes Reaction with

derived

of LiCHBrF

respect

Referrncesp.52

from
to olefin

various

:CHF)

with

configuration

the preparation

lithium olefins

of some

fluorocarbenoids

c671.

is stereospecific

and 'stereoselective

with

W.H:$& '.. ._ .

14

preference

8rCH’

-

BuLi

The

system

trans-4-octene

EWCH

_

‘F

is quite

H

H F

Pr

complex,

fluorocyclopropanes

__:

Pr

Li

‘F

;. ._

c681:

to the syn-fluorocyclopropane er

:

however,

and low yields

~.

of the

are the result.

The reaction

of LiCC13

with

Q-halonitrobenzenes

a,a-dichloro-S-halo-Z-nitrotoluenes

in quite

yields

good yields

C&91. :

LiCCts

-70”

c

THF

CHC’2

i (X=F.CI.Br.t)

Carbenoids trans-XxX11,

derived

yield

Br

from gem-dibromocyclopropanes, products

different

indicating

MeLi ---------cR (R-t-Bu)

Br

cis- and 7

that no

products

from

cis

products

from

tram

cis-XXX11 =#= Li

Br

crossover noids

occurs

prepared

stabilized

(e.g., through

from compounds

by the neighboring

as nucleophilic

reagents

-

Carbe-.

1,2_cycloheptadiene).

such as XXX111 oxygen

and XXXIV

and therefore

Ci'l, AS 68, 2061:

are

are useful

.~

15

c Br

._Br

0

XXXIV

CL

Li

_-CL

stBo/-ao~ -f?%

0

Ts

__C’

MeLi

0

xxxv

The

dichlorocyclopropane but

carbenoid, high

preference Ph

XXXV

also The

in low yield.

to the carbenoid

Ph

Ph

yielded

a relatively

dichloride with

XXXVI

a quasiaxial

stable

leads C-Li

with bond

Ph

XXXVi One

is tempted

XXXVII

with

The ported

to suggest

the TF electrons

first

interaction

of the

of the neighboring

1-chloro-l,l-dilithium

compound

lithium

benzene has been

1731.

CiCD,S02N n

2n-BuLi THF/-75O

Refeencesp.52

atom

UP (94%)

in

rings. re-

c723.

W~_-&&j:;

16

Other

gem-dilithium

compounds

PhCH

CN 2

2.3 n-8uLi THF/hexane

PhCLi&N

c

-

40

PhCD&N

(90%!

25O

2.5 n-6uLi

PhS02CH2Ph

dilithio CH,CN

+

020

PhS02CD,Ph (94%)

of acetonitrile

derivative

-

PhS02CLi2Ph

THFjhexane 25”

Polylithiation

(no evidence

t-BuLi/Et,O

-

for Li$CN).

Li2CHCN

+

LiCH,CN

I

(LiOCHMe),CHCN

Me,SiCl I MegSiOCHMeCH2CN (10%)

(70%)

of 5% (Me3SiOCHMe)$N

metalation

of

derivatization. also

investigated Further

either

spectra

and the principal

or (LiOCHMe)LiCgHN

CAS 70;

2721.

species

yield

aminomethylcyclohexanoles

yield

2-unsubstituted

oxazoles

Cyclic

were

identified.

for synthetic ketones

with

c761 and acyl halides C773.

during

of metalated-nitriles

use of isocyanomethyllithium

has been reported

below:

from the system was attributed

(LiOCHMeI2CHCN

The infrared

CH,CHO

LiOCHMeCH2CN

Me+iCl I (Me,SiOCHMeIzCHCN

formation

the corresponding

C751 produces

CH&HO c

to

_-.

C741.

et al. --

The

:

by Kaiser

have been reported

.‘..

Two examples

tiere '.-

purposes

LiCH2NC or amides

are given

..

17

LITHIUhl

y-c 0 MeOH

(11 LiCH2NC

HCI

(2) H+

::

PhCH2-C--Me2

a-Lithiated utilized useful tion

-

as evidenced

also been

derivative tertiary

acids

butyl H

_

The

The

has been

of tryptamines stereochemical

I?20, MeI,

..

A

are also

and

in the with

of the reaction

of

(dehydroisoandrosterone) of the a-lithio

of BuLi with

-LiCl

-

a-chloroethyl

[Sll:

t-B”OO?Me

AI XXXVIII

N,N-dimethylacetamide

PhCH2:CH

be

in the prepara-

by condensation

suggested

-Me

also

acids

[781,

intermediacy

Li

&

synthesis

acids

ketone

C801.

t-8~00~

use

aeration

from the reaction

peroxide

n-BuLi

t-B”OO?-Me

Lithium

by

may

carboxylic

stereochemistry

to a cyclic

reported

XXXVIII

The

C781.

esters

by their

of B-hydroxycarboxylic

dilithiopropionate

with

Lithiated

of a-hydroxycarboxylic

compounds

O+N

-propionic

and

reactions.

intermediates,

carbonyl

-

(47 “lo)

isocyano-acetic

preparation

has

PhCH2-C-CH,NC

(2) H+

in these

phCH2m

i?

(1)LiCH2NC

MeLi

Referencesp.52

also

been

utilized

for the

C823. course

and ketones

3 THF.-60’

has

of reactions

has been

of a-lithio

established.

sulfoxides

W_H_.G&. ;.

18

Assuming

that deuteriation

with Me1 must action

with

sultones

occur with

ketones

have

ference

Moreover, axial

studied

(1)

BuLi/THF

(2)

Ha0

H

Re- '. .-

a-Lithio-6+

[841.

apparently

in the equatorial

position

rearrange

upon brief treatment

isomers

c831.

in the same laboratory

There

and XL rapidly

then reactio&:,

of configuration

of only equatorially-substituted

XXXIX

a:

with retention,

with retention

51 above].

for lithium

the formation

inversion

occurs

also been

[SS; cf reference

proceeds

‘i. :, ~. -. .

-

is a strong

pre-

as evidenced

by

derivatives.

to the corresponding...

by BuLi/THF.

e:“’

Me

XXXIX

Ph

-._..

The author

estimates

XL is more

stable

more than that

by approximately

benzylamine

in the equatorial 2.7 Kcal, which

found for cyclohexyllithium

Halophenyllithium for benzyne,

that lithium

compounds

as, for example, f8Sl.

continue

position

_’ -,

of

is appreciably

compounds. to be used as a source

in the addition

to N,N-dimethyl-.

‘.-_ _.

19

LITHIuh4

Q BuLi QLi = F

CQT

F

radical

pair

XL1

of XL1 to the major

by thermal

workers

consider

process

rather

should

c871

lithium

halide

than

be noted

Coupling

reported

XL11

of o-halophenyllithium

analysis

explosive

disilanes

product

occurs

via a

process.

The decomposition

The

‘Me

Me'

XL11

The rearrangement

1‘Ci-iiaPh Me

Me’

Me

gated

$__@

a two

step

tendency

and KMR methods elimination ionic

C881.

area

of pentafluarophenyllithium and

These

process.

in this

perhalo-di-

investi-

to be a synchrono-as

of polyhaloph~nyllithium

by all workers

and with

has been

compounds

[89,901!

with

poly-silanes

two methylchlorohas been

c9ll: tF5CG)Me2Si-

Me,Si-SiMe,(CsF,) Me3SiSth4e;\

o

SiMe,(CsF5)

/le*Si-SiMe2CL

0 l-1 Si,CI,

Or

(SiCl,Ix

i (CGF,I,Si

With

halogenated

olefins,

pentafluorophenyl-fluorine ation

and

References p. 52

elimination

C6FgLi

gives

exchange,

to the

products

sometimes

corresponding

corresponding followed

acetylene

t0

by metal-

1921:

20 ~.

C6H5CgF4CgF4CX=CYZ CsF5Li i C6F5-C6F4-CX=CYZ

1

CgF5Li

CXF=CYZ

CBF5Li

CsF5CX=CY2 RLi i C6FsCX=CYLi -LiX

1

CsF5Li ___L

C,F,ECY

Various

have been reported

of c6c15Li

with nitriles

Also reported

c94, AS 70; 211.

cess BuLi yields

I& 0

Lithiat

variety

the dilithiated H4=-

(11 BuLi (2)

CO,;

on

have also appeared for the prepara2-substituted

of 2,3,4-triiodofuran species

with

ex-

196‘J:

0

CO,H

ion of 4,4*-dibromooctafluorobiphenyl

of products

details

1

I c\r

H+

More

c931.

from penta-

c957 and various

The reaction

derivatives.

prepared

were procedures

tion of trichloro-2-thienyllithium silane

5 C Cs F5

of tetrachlorobenzyne,

adducts

chlorophenyllithiurn, the reaction

CgF5C

depending

on the reaction

leads to a temperature

[97_,

AS 70, 2741.

I

2 euer

(30%)

Furan

adducts.were

benzyme

formed

intermediates.

which

revealed

(19%1

the presence

of several .:

21

LITHIUM

Tetrabromo-4-pyridyl fashion

[981.

derivatives only

.However,

react

the 4-methoxy

with

BuLi

compound

in similar

yielded

a

R Br

n-BuLi Et,0/-75°

Br R = OMe.

NMe2 .C5H,,N

furan

adduct.

Tetrachloro-2-pyridyl

ducts

characteristic

derivatives

of halogen-lithium

Cl

also The

exchange.

Li

gave

pro-

authors

H HO

2 R =OMe.

have

NMe2.C4HeN,C5H,oN

summarized

pointing lithium

the results

out the exchange

factors

of several

which

determine

pyridine

derivative

yields,

the

of this

site

type,

of halogen-

[AS 69, 221.

4-Lithiotetrachloropyridine trimethylsilyl

studies

after

has been

C993.

With

reaction

with

derivatized

excess

t-BuLi,

MesSiCl,

to the

4-

pentachloro-

a tris(trimethyl-

silyl)-derivative. Lithiation been

used

to prepare

derivatives Decomposition to occur

of the

of XL11 of the

fluorinated

a number

of derivatives


via a transient

hydrocarbon

reported

derivatives

bridgehead

XLIII [1003.

Similar

in another XLIII

radical.

has

(R = F) has

paper

been

ClOll.

proposed

W.H.G&-

22

._-

R’= 0.Me.Br.f .COrH. CH(OH)Me. CH(OHlPh, C(02CMe)=CH2

has been prepared

Pentafluorylpropenyllithium tion of a 1:l mixture

-3 F’

of XLIV and XLV with

by the reac-

BuLi c1023:

F ‘czc’ Xl_.lV

‘!I [CF3CF=CFCil xLvl

The yields

of the carbinols

of stereochemical action

identity

were

of XLVI

and elimination

products

H Ph’

*\ Ph’

lH cc,

RLi

r

‘c=c/

H

with retention

isotope

effect

although

yields

C1033.

‘c=c<

RLi

-Li

R

The re-

a mixture

The olefins

of sub-

are

for elimination

H

‘c=c( Ph’

F H

H

of configuration.

a direct

the reaction.

loss

‘R

Ph’

formed

50% indicating

H

Ph-C3C

F

than

during

of cisand trans-styrylfluoride -

stitution

cess,

greater

indicates

E2 process

cannot

A large a-hydrogen this to be an E2cb probe ruled

out for the

trans-isomer IV.

Lithiations Several


groups

have continued

Exchange

Reactions)

to exploit

the metalation~of

. ‘~ i

..

LITHIUM

23

organic

materials

activated has

by diamines

and

lithiated

products

As many

indene

were

complexing

from

atoms

anthracene,

per

(fluorene

with

t104'1

biphenyl,

The

- TMEDA.

by reaction

when

Halasa

agents.

from n-BuLi

were-examined

particularly

poly-

I)20 and Me3SiCl.

or anthracene)

mole-

indicated.

recently

and

coworkers

by the

also

study C106l.

the

perlithium

second

reported

the three

of derivatives

C5H4

are

contributed

with

below;

at least

from the Quenching

compound. shown

to this

area,

phenylpropynes

obtained

C5Li4,

isomer

formed

have

of polyiithiated

and penta-1,3-diyne

yields

compounds,

products

prepared

as ten lithium

R. West most

and other

exami,ned the polylithiated

fluorene,

cule

by organolithium

with

diyne, with

D20 the

66% of the

Cl051

water

same types

species

H-CZC-CZC-CH, (5%) n-BuLi

H-CZC-C-C-CH,

“C&_,;’

TMEDA

-

Hz0

H-CSC-CH2-EC--H (20%) H-CSC-CH=C=CH2 (1 5 %J

four deuterium C9Li6H2

atoms.

and C9Li5H3

With

1-phenylpropyne,

species

as the major

one obtains

products.

No TMBDA

":-~=a~.-i~'r'_:~:_-:;~-. ! -_

x

11) 80948 (2)

D>O

hr

%

T

20

4 5 6

32 38 8

I-----Ph-CEC-CH3 Ph-$=C=C

i SiMe,J,

SiMe, I-

$&=C=C( 3

SiMe3l, SiMe,

Me3Si

SiMe3 Me3Si

Rczferencesp.52

0 Q-

k=C=C(SiMe312 SiMe3

is

having

or other

complexing

of polylithiated

of the agent. have

2783.

species

this

rapidly,

system

The former

tive of 1-phenylpropyne

with

is decreased

reacts

the rate o~:...~. z.;'_

such agents,

.the..

due to metalation.

cl071 and Balyan

under

have

but that reaction

so that Me3SiCl

Although

is accelerated

Klein and Brenner

investigated

EAS-70,

is required.

of the propyne

metalation yield

agent

somewhat

;i

et al. Cl803 ..:

milder

conditions

shown that the dilithio

deriva-

with

bromide

one mole of methyl

with a second

mole

is slow enough

may be used to trap the half-.methylated

product

c1071:

I

PhCHCZC-H

MeBr /lel.ei., 2 n-BuLi

Ph--CC-CH,

PhCZC-CHL$

- 50 qEt20

Ph;;;C+

I

h

“r’”

PhCH-CEC-SiMe-, (80%)

(2) Me$iCl

The authors position propyne

conclude

followed XLVIII

Ph--CC-CHLi2

that methylation

by rearrangement

by hydrogen

-

MeBr

occurs

at the benzylic

of the mono-methylated

lithio-

migration:

[Ph-$I=C=CtiLi] Me XLVlIl

_

PhCH-CIC-Li Me Me3SiCI I PhCH-C_C-SiMe3 t&e

The present in this somewhat

data regarding

system,

whether

confusing

The-lithiation

the nature

allenic

of the lithiated

or acetylenic,

species

is incomplete

to this reviewer. of 3-methoxy-1-phenyl-1-propyne

and :

under

condi--'.

LITHIUM

25

tions similar to those derivatives pound

$s the major

IL, which

products

the authors

be sequentially Ph--CC

used by Klein

and

Brenner The

[109].

yields

allene

dilithiated

com-

as an allenic derivative,

write

may

alkylated as shown below: 2 n-6uLi

-CH,OMe

EbO;

[Ph-C=CI;C-OMe]‘?2

-75O

RX

Li@

I

RX

/ Ph\

,OMe

OMe

,c=c=c\

:C ‘C(

R

R’

R

t-l+ Ph

‘CZC’ R’

H ‘CHO

Yields

of the allenes

CR = Me,

ported

between

82%.

a-Ethylenic

yield

by acid hydrolysis

were

prepared

alkylated

70 and in high

S%e9;

R' = Me,

SiMe9)

aldehydes

were

re-

and ketones

of this mono-

product.

Hetalation laboratories.

of enynes Klein

MeLi

to monometalate

ates

the

same

and

has

been

reported

from

two

cowol?kers Cl.10, AS 69, 261 have used

a series

substrates).

also

of enynes

The major

(BuLi quickly

products

from

dimetal-

protolysis

Ph ‘c=c=c( H’

H CH=CH2

PhCCC-CH=CHCH3 L (31%)

Lie PhECCH2CH=CH2 L

MeLi 25O; 6 h

PhC&HCH=CH2 MeBr I PhCEC-CH-CH=CH tJAe LI MeLi i PhC?T.-~(MeJ-CH=CH2

References p. 52

LII

Hz0

/

Me,SiCI \

Ph 2

Me+i

H ‘c=c=c( / (70-80%~

CH=CHz

(46%) (23%)

and

silylation

the

unconjugated

was

also

ture

were

enyne

examined

Also

by

the

reported

its

PMR;

chemical the

methyl

monometalated

spectrum

smooth,

shifts

of

metalation

of

polybutadiene

efficient

diphenyl-1,4-phenylene and

no

trast

to

cl131

that

was

the

gave

only;-.: >' of .LI,.‘- ...

derivative consistent

delocalization

of

olefin

with

charge

and

struc-

was

aromatic

of MeCSC-CH=CHMe

and

and

were

processes

polyisoprene

if n-BuLi/TMEDA

Poly(Z-methyl-6-phenyl-1,4-phenyene

THF

bromide

in;

protons.

L1113.

Lithiation be

The

LI.

substantial

was

EtCZC-CH=CHMe

to

by

LII,.although

dicated

whereas

allenes,

chain

ether)

scission

lithiation LIII

of

Cl141

takes

disnes.

(R=R'=Me)

ether)

cl131

lithiate

more

place Very

apparently

in the

was

used

and

poly(2,6-

easily

process

interesting metalates

reported

in

in con-

is the on

c1123.

report

a ring

R

B-f 0

O

R’

x

R =Me.Ph; R’=Me,Ph LIII

position

initially,

but

isomerizes

to

side-chain

metalation

with

time. Lithiation folloued for

the

by

of

a series

condensation

synthesis

of

some

of methoxy-substituted

with

Me2C=CHCH2CH2COMe,

aromatic

Me0

Li

has

derivatives

MeaC=CHCH2CH,CMe

benzenes, been

used

Cll51.

B

OMe Me-C-OH &&H&H=&e2

L.In-IIIJM

27

Reaction exclusively reported

of the olefins

LIV with

the mono-lithiated

earlier.

side reaction

In Et20,

as shown

Ph+‘”

products

in THF

whose

addition

however,

Cl161

spectra

yields

have

been

is a significant

below:

Etn-BuLi

PhAph

+

Phhph

+

2

R

n-BuLi

(R=H.MeJ

(L max 333nm)

LIV

tl max 478nm)

LV

LIv+Lv

Ph

LV (1,,,~333nm)

Also

The

c1171, with

reported

intermediate

several

PhCH,NHR

was the

between

LVI were

amines

derivatized

ketones. n-8uLi/TMEDA

PhCHLiNHLi LVI

of LVII

was reported

the substituents(*)

to occur

only

if n-BuLi/TMEDA

at the positior

was used

CllSl.

NMe2

CF3

LVI

LVII

With

n-BuLi/Et20

LVII

with

References p.52

of some benzyl

dilithioamines

(R=Me.Ph)

Lithiation

lithiation

a mixture

n-BuLi/EtpO

gave

of products mainly

the

(unresolved) results. \ 4-lithiated product. Also

W.H.GiAZE

28

reported

Cl191 were

lithiations

.dimethyl(naphthylmethyl) V.

Reactions

Two reviews

have appeared

compound

initiator

Unlike

c1221.

has been

by Halasa

approximately

corporated

into the polymer

yields

by

and o- and p-chlorostyrenes

studied

the unsubstituted

Polymerization

initiated

of 1,3-butadiene

activities

NaNaph

on polymerizations

t120, 1211.

Copolymerization with n-BuLi

N,N-

amines.

Polymerization

organolithium

of some ring methoxylated

:

these

case,

and coworkers

styrenes

equal to that of butadiene chain with

of the stable

a paramagnetic

uniform

radical

polymer

have re-

and are in-

distribution.

LVIII

with n-BuLi

of low molecular

or

weight

c1231.

5H=CH2

I

I

pVfNWN'Ph LVIII

Also reported dimethyl

ketene

is the copolymerization

with benzophenone-Li

was shown that ketene

addition

Inthe

of optically

polymerization

propyl)-1,3-butadiene fic rotation

of the polymer

adduct

takes

with n-BuLi

of p-anisaldehyde

place

Cl243

active

across

in which

and it

the C=C bond.

Z-C(S)-l-methyl-

in n-heptane

c1251,

was of the same order

the speci-

0% magnitude

as that of the monomer. The reaction

of alkyllithium

compounds

followed

by addition

of styrene

grafting

of polymers

to the carbon

method

is superior

functionalities

to reaction

which

with

or isoprene, black

may be introduced

results

surface

of "living"

cakbon

in the

C1261.

polymers

black,

with

on the carbon

The es&

surfa.&g.‘

LITHIUM

29

BuLi-initiated THF yields

increasing

servations

to near the

amounts

A steric

is lowered.

addition

polymerization

C1271.

of 1,2-addition

argument

was

in benzene

zero as the temperature

ionic

character

used

of cis-1,4

was

found

was

increased

of the aryllithium

in

as the temperature

to rationalize

the ratio

Similarly,

of isoprene

of 2,3_dimethylbutadiene

to 3,4-

to decrease Cl281

initiator

the ob-

from s 280 and also

was

as

increased

c1293. Isoprene -lithium

initiators

or styrene Other

produced

reports

appeared

monomers

with

and

methacrylate

phenyl

and methyl

1421.

The

C1331;

lithium

metal

oxygen,

concerning lithium

methyl

t136J;

vinyl

last report

(presumably

VI.

with

oligomeric

di-

and a diene

cl303

the polymerization

sulfones describes

carbon

methacrylate

a-phenylacrylate

cyclic 11391;

sulfides and

the effect

dioxide,

(2-methoxy)-

initiators:

(2~dimethylamino)ethyl

3-methyl-but-3-ene-Z-one

rates

from

have

methacrylate

methyl

copolymerized

t1313.

of the following ethyl

and

was homo-

C134, t137,

styrene

C1323; 1351;

1381;

Cl40,

141,

of impurities

and water)

on polymerization

of polystyryllithium. Reactions

with

Heterocyclic

A new procedure

Compounds

for the preparation

phenyl-1,2_dihydropyridines

has been

of M-substituted-2-

developed

which

the reaction

of 1-lithio-2-phenyl-1,2-dihydropyridine

acid

[l&3,

halides

AS

L

LIX

Referencesp.52

70, 2893:

.R I

involves LIX with

W-H_Cm.

30 The

S-C-substituted

becomes

the

derivative

major

direct

formed,

and

with

R = .C.Fi- 1 . - . . .:

were

prepared

product.

2,6-Di-t-butylby

is also

and

alkylation

by

2,4,6-tri-t-butylpyridine pyridine

; : :_I::.. :

.::

[1441:

(1) t-BuLi (21 Hz0

The

mechanism

lithium PhLi

has

with

been

of

the

reaction

reexamined

lepidine

was

or

methyl

cl451.

proposed

quinolines

The

to be

(LX)

phenyl-1,4-dihydroquinoline

of

initial

with

organo-

product

from

l-lithio-4-methyl-4-

which

_may rearrange

by

phenyl

migration:

6

PhLi

_

&h

CICOzEt_

fi

Lie LX

(1)

H+

(2) co1

Me

(1)

H+

(2)

co1

Ph

Me (99.5

Also lithium

%I

(0.5 %I

prepared

wigh

were

adducts

of

alkylthiovinylacetylenes

a-picolylE146.I to

and

2,6-lutidyl-.

yield

allenic

'thio

esters: ..

CH,=CH--CC--SR’

.

CH2CH2CH=C=CHSR’ R=H,Me

(R’=Me,Et

1

. . ..;:...-.y’._

31

LITHIUM

Pyrazine, with

MeLi,

ated

and hydroxylated

probably product

EtLi,

and

products

were

and

Some

[1471.

also

subsequent

found,

react

the

oxidation

dialkyl-

latter

of the major

LXII. 2-alkylindazoles

in the

l- and

Furoquinoline involving LX111

2,5_dimethylpyrazine

P-methylbutyllithium

due to lithiation

l- and marily

and

methylpyrazine,

is shown OMe

3-positions

alkaloids

lithiated

have

have

intermediates

been

shown

to metalate

respectively been

cl48,

prepared

[1501.

The

pri-

1491.

by a new route route

to dictamnine

as an example. (1)

n-BuLi

I

-H2

Halogen-lithium 5-lithio

exchange

derivatives

of some

has been furfural

utilized acetals

to prepare ClSl3.

These

n-BuLI CH(OEt12

CH(OEt12

subsequently sponding More

carbonated

cadmium

reagents

information

Referencesp.52

and aiso with

on the

used

to prepare

the

corre-

CdC12.

stability

of 3-benzo[blthienyl-

the were

32

WH.Gti

lithium

has appeared

cblthiophene hydrogen

when treated

with n-BuLi

as well as halogen Br

undergoes

exchange

3-bromoben&oi-

In THF,

c152, AS 70; 2901.

lithiation

by:.:.

reactions.

(11 n-BuLi (2) CQ,;H*

The

lithium

precursor

halogen-lithium of LXIV with tions

exchange

compared

New routes

directed

reaction

LXV presumably between

have been revealed

MesSi

and Gierer

cl531 by

Ph*CO)

of 2,5-bis(trimethylsilyl)thiophene the expected

3-lithio

and metalation

1

R&NMe2

sRdNMe2* (E=

groups

reac-

reactions.

(R=Me)

of -SiMe3

of methylation

(E= D~0,HCONMe2.PhZC0.PhCN

R&NMe2

does not yield

precursor

and 2,3,5_trisubstituted

by Slocum

(X= NMe,,OMe)

Reaction

from a

in ether and THF in this paper.

to 2,3+iisubstituted

metalation

comes

the lithium

Yields

3-benzoCbjthiophene.

also were

thiophenes

of compound

derivative;

are the result

Me3Si

f\ l-l s

.~-

with n-BuLi/THF rather, C154l:

Sic

M@

Ejle CH2Li

cleavage

UTHluM

33

Metalation rather

Also

than

of 3-benzylthiophene

at the benzylic

reported

by the

same

position

group

of two phenalenothiophenes exclusively

occurs

or on the benzene

was the

LXVI-LXVII

at the benzylic

on the thiophene

synthesis

position

[1553:

and netalation

Each

C1561.

ring

ring

metalated

("1.

&3

I---

S

x

LXVI

I

.

Competitive reported

by Gronowidz

at the bridging (16.8);

fluorene

Several Kauffmann cl581.

References

metalations c1571.

methylene (371);

p_ 52

The

were

examples

using

are shown

with

relative

found

various below:

were

have

been

of metalation

LXVIII

(754);

compounds

EtLi

rates

to be:

3-methylfluorene

thiophene-pyridine

and associates Some

of LXVIII-LXX

LXX

(1);

(1360).

prepared

organolithiums

LXIX

by

en route _P

Similar

couplings

between

were also reported A rather

bithienyis

difference

in their

Cl661.

and quinoline

ring

systems

C1591.

striking

been demonstrated

thiophene

between

reactions

EtLi gave

EtLi and n-BuLi

with

has

some dibromo-3,3'-

55% LXXI and 45% LXX11 while

n-BuLi

gave only 10% LXX1 and 90% LXXII. Sw AS

al-

(11 RLi/EtpO_

I

(2)

CO,;H’

Q-q

Br

+

h’opc

Q-Q

COzH

CQH

LXX1

Lithio-1,3-dithianes mediates relate

continue

[see Hechanisms

section

to the reactions

of these

Cl611 and to the relative six membered VII.

rings

Addition

Reactions

to serve as useful

above].

Mew reports

compounds

tendencies

containing

Br

LXX11

To - Carbonyls,

this year

with aromatic

of metalation

two sulfur

inter-

atoms

Olefins,

halides

of five and-

t1621. and Similar

Substrates Further compounds abovej. these

work has appeared

to vinylacetylenes The following

reactions

on the addition

of organolithium

[AS 69; 35, also see 110-111,

reaction

sequences

for the preparation

illustrate

of various

allene

146

the use of derivative&,!

35

LITHIUM RC,H,Li

(R = p-Me,m-Me.p-OMe; EtLi

+

*20

-

+ CHz=CH-CGC-SR’

-

R’= Me,Et -

CH2=CH-CZC-Et

RC6H,CH2CH=C=CHSR’

)

Cl631 /Et

EtCH&H=C=C, LXX111

OLi b&O-;-H

H

I

Et

Et

EtCH2~=C=2-CH-~=C=CHC~E~

-

AH

(1)

txx111

/Et

EtCH2CH=C=C,

12) H&l

c=o t:

cl641 LXX111 + t-BuOOH

-4o_

0

?H EtCH&HCGCEt

5! + EtCH&C=CEt

B

+ EtCH&H=CH-C

-Et

cl633

Cinnamyl

ammonium

allyllithium process

to

yield

salts

have

been

cyclopropanes

by

reported an

to

react

with

addition-rearrangement

cl6512 I@ + CH+ZH-CH2Ci

PhCH=CH*-CH$RJ,

L,@ o--x

Ph-CHFHCH,F3R,.I

Q

0

CH2CH=CH2

PhCH-

1

CH2

‘CL CH2CH=CH2 (35

Metalation

with

%I

subsequent

Stephens

rearrangement

is a competing

process. The

neutral

cinnamyl

a straightforward

addition

(I) RLi

PhCH=CHCH2NMe2

With

primary

following References p_ 52

with

n-BuLi

and

t-BuLi

by

r-1661:

PhCH2CHCH2NMe2

I

R

excess

(shown

reacts

process

c

(2) H20

amines

route

amine

for

RLi

yields

ketones

a-methylbenzylamine):

presumably

by

the

W.l-l:G&kE

36 NHz PhkHCt-$

-

NLi2

2 RLi

Ph:HCtf3

-

iLi

-LiH‘

Q PhCCH, (6 %I

‘-‘zO_

PhCCH, RLi yLi2

‘;JH2

‘-‘20

Ph-F-cH3

Ph-C-CH,

-

R

A

(25%)

The reaction by oxidation mixture

of isoprene

with molecular

of at least

eleven

tion of the intermediate ketones

and epoxides

Also cl.697.

reported

lithium

oxygen terpene

anions

6

alcohols

follotied to yield

a.

Derivatiza--.

C1671.

has also been carried

out with

Cl68l.

was the addition

of RLi to benzonorbornadiene the reaction

of t-BuLi

n-BuLi

1

and n-BuLi

naphthalene

has been reported

In the same paper was described

‘1

adduct

with

r

with

‘\ cA

oxide

LXXIV

Eu

in

which

of the initial

ring-opening

occurs: 0

/\ @

\

&” -

%y-

q;”

LXXIV

n-BuLi /

Excess

n-BuLi

caused

the formation

Li@

I

of a diadduct

H2°

due to addition .- __-

to the C=C bon.d. Other

reports

have also appeared

colioerning additions

ofi-:-.r -.

37

LITHIUM

MeLi

RLi to epoxides. activity

with

magnesium that

cyclohexene

and copper

it

only

gives

and PhLi have

1,4-conjugate

addition R=Meor r

in sharp

MeLi

contrast

With

compared

compounds

as well

LXXV,

give

C170,

in their

corresponding

the trans-1,2-addition

methylmetal

LXXVI,

to the

compounds.

and the other

With

oxides

been

re-

organo-

MeLi

is unusual

in

product,

whereas

PhLi

products

arising

from

1711:

Ph_

gives

75% benzene

to MeMgCl,

hydrate

Me2Mg,

and

25% benzene

c1711,

and Me2CuLi:

QoH+0

0IO-==--

LXXVI

1,6-Addition

0

to LXXVII

f

MeLi

has

been

apparently

D

of the trans

References p.52

reportedly

on the

in a cis-fashion:

D

product

was due to the

Chloroepoxides depending

to occur

__c

D

Formation

shown

as indicated

presence

react

substituents

of

with

present

in an earlier

halide

PhLi

in the MeLi.

by different

[1733:

report

routes

_-.-

0

Ph Ph-&-cH=CH2

+

MeT/~;c5H11

::;

pH$i

(40%)

LXXIX

(60 “lo) rh

‘5H,,-$

..’

-

AH

LXXVIII

__

Ph-?-CH2CH2Ph

-CH=CH2

?

C,H&

C

CH2CH2Ph

+

2 C,H,,CCH

(Me) Ph

HO

(80

Products by

LXXVIII

and

LXXIX

%I

arise

a deprotonation-elimination

from

RCOCH=CH2,

which

is formed

’

process:

-.

0 R-&H=CH2

Reaction

of

continues

to

EtLi

Z-methylcyclohexanone

with

be

organolithium a useful

compounds

synthetic

with

carbonyl

procedure.

and

LXXX

The

compounds.

reactions

reportedly

of

yield

0

.fl

Me “: Me

CH2-CH=CH2

LXXX

volatile

products

consisting

presumably

via

a radical

of EtLi

the

C=C

to

hexanone ketone yield

C174, (e.g.,

$-hydroxy

LiNaph

+

of

the

Reaction

cyciohexanone) acids

E,

process.

bond

1751.

of

C2H4, Also

sodium of

and

C2H6, reported

enolate

lithium acetic

of

CH,COOH

-

acid

Q

HO

n-C4Hlo;

was

was

CH$OOH

the

addition

2-methylcyclo-

naphthalene

C1761:

+

and

with

reported

a to

.

39

I..lTHIuM

The

stereochemistry

isomeric

of

additions

methylcyclohexanones

has

of

been

PhLi

to

reported

the

three

c1773.

OH

OH

0

13

PhLl

(56=&J

Me

(44%)

r-_$h

-I

4"

Mew

k-----J

(47 %I

Reaction However,

of

LXXX1

reaction

with

c-

o ;/

Also

reported

NMe*

‘NMe2

with

Me

cyclohexanone

aldehydes

can

(11 RCHO (2) heat

(53%)

could

occur

to

not

be

effected.

give

alkenes

Ci783:

with

MeLi

shown

CHR

-cl=

LXXX1

was

the

reaction

of

LXXX11

as

11793:

@ZzMe MeLi_ g-p’ + LXXX11

The lithium

preparation compounds

Jorgenson lithium

11801. has

principle

References p. 52

been

c1811:

of with The

ketones

from

carboxylic reaction

utilized

to

of

the

acids the

prepare

reaction has

ester

been

of

reviewed

LXXX111

B-damascenone,

organo-

with an

by allyl&

odor

WXG&&

40

L--Et

,

G LiCH2CHzCH2

LXXXlIl

Alkyllithiums produce

ketones,

mechanism as

with rather

proposed

shown

B-keto

below

than

involves

for

ethyl

esters

were

found

to

undergo

metalation

the

initial

formation

a-n-butyl

(18

of

Addition LXXXIV

+

of a f3-diketone

alkyllithiums

to

corresponding

en

8

aucau (8%)

(6%)

(24%)

the

yields

a CH3CCH2Bu

‘3”CH2$Bu

%I

The

C1821.

%Q 0

+

tc

acetoacetate:

H20 0 CH,tB”

unexpectedly

bridged

lactams

such

as

namine

in-very

high

yield

c1831:

a’

MeLi_

Ph

me Ph

o

CH2

LXXXLV

EtLi

9-Methylanthracene

is not

in THF

both

cis-

are

formed.

C1841,

i.e.

9,10-dihydroanthracenes

stereospecifically and

alkylated

by

trans-9-ethyl-lo-methylA radical

pathway

to

these. .:

products was proposed: RLi

+

ArH

_

ArH-.Li+

R-

+

AI-H

--) f-

R-Ar-H-

RArH

+

RLi

-

RArH’,

+

R. _,

Li++

R-

; ._..) .. _. -’

Li'l-HIUM

41

Reaction to occur

of arylsulfonium

by addition

predominates

compcunds

at elevated

at -7OOC

with

BuLi has

temperatures

whereas

been

found

metalation

c1851:

n-BuLi /

34O LXXXV

The

intermediate

LXXXV

was

trapped

with

D20

(as

shown)

and with

co2.

Miscellaneous

VIII.

Photolysis reported

detail

Cl873

does

(2,2'-dimethoxybiphenyl), primary

Reactions

of aryllithiums

in more

anisyllithium

Organic

product.

The

[lSS,

to produce AS

65; 151.

not yield however;

intermediate

much

biphenyls Photolysis

coupling

was

OMe

l-i OMe

OMe hv Li

LXXXVl

(17 %yo)

References p_ 52

of o-

product

2-methoxybiphenyl LXXXVI

has been

trapped

is the with

carbon

WSI.CL+

.: :z. ._.

although'not.

:

42 dioxide

A benzyne

and D20.

proven

was postulated

.’

conclusively.

A new synthesis cidated ally1

mechanism

[1883.

anion

of u,6-unsaturated

aldehydes

Reactions

of LXXXVII

SMe

Hg*2

R&iCH=CHSMe

-.

is the 1,3-bisCmethythio)'A

The key to the synthesis

LXXXVII.

has been elu-:

with ketones,

c

RCH=CHCHO

Lie LXXXVII

aldehydes,

and epoxides

The reaction proceeds

aldehyde,

of s-BuLi

in somewhat

isonitriles

were

also reported. and l,l-diphenylethylisonitrile

unexpected

fashion

C189, AS 70; 2961. three

other

products

as compared

In addition were

isolated

to other

to Z-methylbutyrLXXXVIII-xc:

Ph

Ph--r--N=C

f

s-BuLi

Me

A?

s_BuCN

CH&H+HCHO

II

s-aul-i _IL)

s-BuC-_(s-Bu)

LXXXYIII

Me

H+

,

I (s-Bu)~C=O LXXXIX Ph&Me)CLi

i-

Hz0

-

Ph,(Mel

CH

xc

With triphenylmethylisonitrile, resulting

from cleavage

UV spectra high

of these

isonitrile/RLi

formed:

the.only

products

of the intermediate adducts

ratios,

have

dimeric

are those

lithium

been reported

adducts

aldimine. C1901.

(and higher)

At

may be, -.

LITHIml

43 C6HI,-N?

+

n-BuLi

-

,5u

C&4,-N=C,

Li

CgH,,-N=C

I Bu-_C=N-CgH,, C=N-C6H,,

Lt -

With

o- and p-isocyanostyrenes,

BuLi or polystyryllithium

only

to the vinyl

further

group

N=C

Substituted diazo

compounds

access

BuLc

by a similar

+

polymerization:

N=C

-

alkyllithium

to a number

Ph&-CN :’

i-

without

adds

compounds route,

of hydrazones

react

thereby

with

aliphatic

providing

convenient

[X911.

~$$&y-@-JIrJ i.j-

N2

A-f-i Ph2:. -CN (11 2!S0(-LiCNl

(2) H,O

tt=CPh2

Reaction gives

of RLi with

3,4_dimethoxybenzyl

3,4-dimethoxyalkylbenzenes

bis(3,4-dimethoxyphenyl)ethane by coupling)

coupling)

(halogen-lithium

reportedly 1,2-

and

exchange

followed

C1921.

The autooxidation reviewed

(simple

chloride

of organolithiums

to peroxides

has been

c1931.

Olefin

formation,

via reaction Referencesp.52

especially

of tosylhydrazones

from with

steroid

hydroxy

RLi has been

ketones,

exploited

W.H. GiAZE

44

C194; AS 68; 2007. however,

further

mechanism

of an excess

In the presence

reaction

to yield

by the following

occurs

alkylated

of alkyllithiti,

products


[1951:

H

Ts -kN

Enediamines formamidinium

have been

salts

The acetarnidinium reaction

ion XC1

is not general,

proposed Reaction

when t-BuLi

to yield

as evidenced was used.

l-Methylcyclopropene chloride

The

by the isolation

A radical

process

case.

cleavage

involving

to rationalize

B-methylallyl

however,

intermediate.

of N,N-dimethyl-N-benzylanilinium

A mechanism

employed

is the presumed

for the latter

has been reported c1971.

by react'ion of MeLi with

El961:

of 81% (t-BuI2CHNMe2 was

synthesized

ion with RLi

and rearrangement

radical

pairs

products

[AS 69; 121 was

the results. has been with PhLi

synthesized

(halide

free)

by reaction [198,

of

see 60-61

above]:

f”3 CI-$=C-CH,CL

Me f

PhLt ‘H 160~f30%1

-..

The attempted pounds

resulted

polylithiation

in ring-opening

of triphenylcyclopropyl reactions

as shown below

comC1993:.

L.ITHIuM

45 Ph (1)

H

LPh H\ ,c=c, CHOPh Ph (90%)

n-BuLi/TMEDA

Ph Ph

PMR spectra

of the

intermediate

H\

+

Ph’

triphenylallyl

CHDPh c=c’

‘Ph ~70%~

anions

were

also

does

not

reported. The reaction

of 1,5-dihalonaphthalenes

lead to the desired rather

the major

conventional New N-Li

have

c2001,

formed

by

including

monoxide

with

C-Li

and

AS 70; 2827.

the use of hydroxyl-tritiated

of these

Inorganic

has reviewed

reagents

has been

reagents

C2021.

and Organometallic

the preparation some

reactions

propanol

utilized

as

Compounds

of many

cr-bonded

involving

lithium

c2031.

Coupling B(OMe13, reported

yield,

[201,

of organolithium

with

organometallics

been

that

for the analysis

Reichle

of carbon

reported

we note

Reactions

BBr3,

derivatives

are diphenylnaphthalenes

reactions

been

for the quenching

‘reagents

PhLi

routes.

Finally,

IX.

products

insertion

bonds

a method

didehydroClO]annulene

with

of CH2Li2

a series

(Me$$BCl

Me2BBr, 12041.

with

The

and Me2NE12)

latter

but the corresponding

of boron

gives

boron

compounds and Me3SiCl

Me3Si-CH2-SiMe3

compounds

(BC13, has

in good

are generally

un-

stable. Reaction the

following

Refmences p

52

of trialkylboranes (proposed)

route

with C205l:

a-lithiofuran

proceeds

by

W.H. GL+

46

+

R3S

OLi

BR,

I R R

*

l_iaO xc111

xc11

HO

XCIV

The

intermediate

cyclic

borate

XC11 or

gives,

be

oxidized reaction

Similarly, lithiums

may

after

“CL&~

quenched

to the of

oxidation,

With

the

the

to yield

glycol

several

dials

XCV

HO

OH

the

XCIV.

phenyl-allylC2063.

(11 BHJTHF - (2 1 .H202

‘G,. xcv

R’=Me)

anion

alcohol

unsaturated

BEI3/THF with

Lie (R=H.Me;

with

of

3-phenyl-l-butene

a mixture

of

products

was

observed:

(11 BH&HF !2)

H202 Me HO (Mixture of Uiastereomers)

t-BuLi borabenzene

c-l ‘Bl I

has

been

c2073:

i-BuLi pentane/THF

utilized

to

prepare

the

anion

of

l-phenyl-

propargylic Anions

ethers

and thioethers

of the type

type

for the preparation tives,

as well as some complex

Two groups

by the reaction

silanes

c224, 2251:

Perchlorinated


of silylated


allene

deriva-

and dihydrofurans.

lO,ll-dihydro-SH-dibenzo[b,f]-

1,3,5_trisilacyclohexane [2261.

of type

and coworkers

of o,o '-dilithiobibenzyl

of products and

furans

have.synthesized

silepin

a variety

by Mantione

of a large number

..

[where

StBu3 and dianions

utilized

:

222, 223, see 109 above]._'.

R-CZC-CH-XR',

= OMe, GtBu,

have been

R-C=C=&XR',

1221,

R-&C=CH-XR'nW

R = Ph, SiMe3 and XR',

to

GLAZE ...-

WH.

48

with

dichloro-

is cleaved

The coupling

reactions

were also reported

by MeLi of

by the same.

C2271. N,N-Disubstituted

prepared

by a transmetalation

RR’NCH2Sn(n-Bu&

The lithiated are readily ception

aminomethyllithium

i-

formed

compounds

through

+

phenyl

(n-6u14Sn

and -CH2CH20CH2CH2->

in high yield,

derivative

have been

c2281:

RR1NCH2Li


of the morpholine

n-BuLi , presumably

_ _

and derivatized

Pentaphenylantimony

t2291:

hexane or THF

n-BuLi

products

reaction

compounds

which

with

is apparently

are "symmetrized"

the formation

the ex-' unstgble.

by PhLi and

of "ate" complexes

.. ..I.. .

LITHIUM

49

Ph,SbMe

+

RLi

_

Ph,SbMe

+

PhLi

Spirocylic

[Ph4Sb
-

_

Ph,Sb
PhSb

i-i+_

antimony

by BuLi to produce

the

+

5

compounds products

f

such

shown

PhLi

MeLi

as XCVII

are also

cleaved

12303:

Li

BuLi

-

Bu5Sb

+

PhLi

i-

xcvir

polyphosphines

Cyclic

cleaved

by PhLi

P(C2H5)Ph

(n = O-3)

expectedly 2081,

which

F \/

F’

‘P

4N ‘N

+ F

/

F

10 IP\

obtained

have

from

are

fashion

1232,

enters

N

F

F MeLi

F’

/

lP\

Me

N

‘N

on the reactions Evidence

of the reaction

The

lpi”

Me

compounds.

Me

BUeMe

AS 68;

,Me

/‘,\

N

F ‘P’

ap/

/\

N4

‘F

Me

of ferrocene for ferrocyne

of 2-methylchloro-

two butylmethylferrocenes

&--

un-

antipodially. Me,

‘P’ N//\F

+

a study

~-B~L~/TMECJA hexane /T H F

,P+

are also

C2H5(Li)P-(PC2H5)n-

F

appeared

C2331.

group

(C2H5P>5

fluorides

in a geminal

\/

N

alkyllithium

and n-BuLi

Me

N

Me

with

Referencesp.52

F

F

papers

of the type

methyl F

N/“\F

lP\

derivatives

ferrocene

by MeLi

MeLi Et20

tC2H5PJlr and

Phosphonitrilic

the third

N\,F

Several

has been

C2311.

F

lp*

as

compounds

dimethylated

after

F

to give

such

were

W.H.GL,AZE

50

formed

in approximately

solvent/RLi

using

(7-841,

1,2-Disubstituted

systems.

been reported

equal amounts

the reagent

but only

ferrocene

XCVIII

in sefekteo

synthesis

has ..

The

r-234, AS 69, 311.

CH2NMe &Li & XCVITI

competition a variety been

between

addition

of solvent

media

explored

pared

used to prepare

a number

of a series

and MeLi has

in high yield,

of symmetrically AsPh2;

n-BuLi

of IC in

1,l' -dilithioferrocene,

PMe2;

of ferrocenyllithium

in the formation

and dimetalation

t-BuLi,

and n-BuLi/TMEDA

(R = AsMe2;

Coupling

and with

C235; AS 68; 1971.

from ferrocene

derivatives

and mono-

has been

disubstituted

PPh2;

pre-

ferrocene

SH) c2361.

compounds

with CoC12

of biferrocenes,

as shown

results [237].

R

The yields

lithiation

of dimethylaminoethylferrocene

of the corresponding

dilithiated

derivatives

were

tions were more rigorous

~CH2NC%NMe2 (,) (2)

Lithiated prepare

benzophenone observed

derivative.

if the metalation

good

Some condi-

C2381.

BuLi

Ph,CO

N-phenylferrocenecarboxamide

the corresponding

gives

deuterio

CI has been utilized

derivative

c2391.

to

1-Lithio-

LITHIUM

51

l'-(trimethylsilyl>ferrocene

reaction

[2401

and used

Fluoroferrocene reaction

have

More

stable

been

prepared

has been

carbene

metal

tuted

C242l;

dry1

Reaction

mercury,

carbonyl

CsFsLi

2 feFgC6H,

compounds:

feHgC6F5 f+Hg

CII, halogen-lithium

lithium

exchange

and

+

(R= H.EW) Cl1

References

p. 52

f

n-BuLi

-78”_

c2411. structures

CR = substi-

ferrocenyl with

12431).

pentafluoro-

of bis(pentafluorophenyl)-

c244.1:

f

LiCl

(=#&‘N

r-2451:

R fe

by the

the appropriate

(or hydrogen-lithium)

was observed

time

following

(C0)5Cr
in the formation feHgC6Hg

first

fluoride

(fe = Fe(C0)2s-C5H5)

-

-

the

of RLi with

R = pentachlorophenyl

results

+

with

exchange

derivatives:

for the

perchloryl

complexes

not the desired

feHgC1

with

by a metal

several

prepared

by reaction

of feEgCl

phenyllithium

prepared

to prepare

of lithioferrocene

transition

With

was

+

6uR

rather

than

iron-

52

.-.

W.Ii.GLAZE~

Reaction

of s-BuLi

radicals,

[2463.

The product yields

transition

metal

PhC ECPh

+

BuLi

when

Also

and

with

reported

was

C2481:

Li+

qp

-

Li

treated

metallocycles

[ wPh]‘2

(n-C5H5)2TiC12

metai

of 2,2'-dilithiobephenyl

C247; AS 67; 1841.

-

stable.,:

to the transition

compounds

of two titanium

+ Li

polyphenyl

halides

La'3 and Fe*3 yields

coordinated

of the reaction

various

the preparation

Cu**,

presumably

organic

CrC13

with

(X-C5H5)

/\ -

‘\

t Z-C5H5)

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1217 36

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93 (1971)

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215 A.V. Ka&ntsev (1971) 1057

26 (1971)_

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22-4 J.Y. Corey, M. 26 (1971) 167

Dueler

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G.

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234 E.B. Moynahan 235 D.J.

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4068 3565 3341

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385 (1971)

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36 (1971)

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28 and

97

64

243

WH.GLAZE;:. .. .'., ,-,

G.A. Moser, E.O. Fischer Chem., 27 (1971) 379

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