Zinc annual survey covering the year 1971

77

ZINC ANNUAL

SURVEY

COVERING

THE

YEAR

1971

Utrecht

(The

Jan G. Nolte s Organis

ch Chemis

ch Instituut

TNO,

Netherlands)

CONTENTS

I.

Preparation

II.

Reactions

of organozinc

of organozinc

A.

Reformatsky

B.

Reactions -carbon

C.

reaction

and related

reactions

Organozinc

compounds

IV.

Structural,

spectroscopic

A.

Structural

B.

Spectroscopic

C.

Other

atom

82

reactions

and alkenylzinc

and carbon-hetero

III.

82

compo?mds

of alkylzinc

Carbenoid

77

compounds

compounds

unsaturated

of organozinc

with

carbon-

bonds

90

compounds

as polymerization

and physical

100

catalysts

105

studies

109 109

studies

110

studies

physical

studies

112

References

I.

112

PREPARATION The

new

1971

organozinc

Referencesp. 112

OF

ORGANOZINC

literature compounds

contains

COMPOUNDS relatively

or new types

few

references

of organozinc

dealing

complexes.

with

78

J.G.NOL~ Lorberth

metal

has published

derivatives

acidolysis

the details of his synthesis Such

of diazoalkanes.

of the very

with diazomethane

reactive

compounds

were

bis(trimethylsilylamino)

or ethyldiaeoacetate

of Group

:.._'-

II B

_~

obtainedby derivatives

LlJ: I

Zn:N(SiMe3)

?!I

ZniN(SiMy)2d2

2

.:

+

CH$$

g%+

+

2HC(N$OOEt

,bnCN2],

%!%

+

. .

ZHN(Si&),

Zn[C(N2)COOEq2

f

+

ZHN(SiMe) 32

Noveltrinuclear characterized spontaneous

by Bdersma

+

n acac'

1

of the

benzene

Hacac

+

S-diketonate

et al. Complexes

disproportionation

P$Zn

2phZ

phenylzinc

P

Ph2Zn

oftype

t

have

been

(I) are formed

Ph2Zn/S-diketone

iPhZnaca4.

f

complexes

via

l/l reaction

PhH

Zn(acac)2

i’

2 :FhZnacaci ‘L +

Zn(acac)2

_3

'PhZnacac]2. !_

Zn(acac)2

(I)

product mixed

or by a stoechiometric

reaction

which

allows

the isolation of

complexes:

.

2PhZnpac

+

Zn(acac)2

w

[PhZn pad 2. Zn(acac)2

-_.

79

ZINC For

(I) a structure

coordinate

terminal

Kawakami weight,

and

e.g.

data)

+

shown

carbonyl

using

f

been

reported

as well

zinc

proposed

of the products

(BuZ2.n

Aminophosphine

P%Zn

have

C%(GOOMe)2

were

o, g-unsaturated

synthesized

has

central [

a study formed

as

-dimethylsilane

b

to undergo compounds

derivatives

BuZnX)

(analytical,

molecular

with active

RNHPP%

%%

MeOZnCH(COOMe)2

a Michael-type

of

methylene

l/l acts

atom

of dimethyl-

baur

and Wolfsberger

complexes as

a

reaction

in which

and diethylzinc

BuH

1,4-addition

compounds

with

have

been

4 -

rJ-

PhZnNRPP%

1,3-bidentate

+

i-31=

of organozinc

an acidolysis-type

zinc

Referencesp. 112

Zj.

by the interaction

f

(R = 2,3-Me&,?,

Crystalline

and two tetra-

:

BuZnOMe

products

atoms

Tsuruta

compounds

compounds,

one hexacoordinate

zinc

IR and NMR

n-butylzinc

Such

with

PhH 4-MeC6H4,

2-pyridyl)

bis-trimethylphosphinimoligand

have

to the tetracoordinate

been

reported

by Schmid-

-80

Me

%

Zn

+

/

M?P=N

(Me,P=N),BiMe2

R

Various

reports

hydridozinc

complexes

Tsuruta wards

carbon

rated

dealing

ketones

et al.

have have

\

‘Zn’ 11

N=PMe3

R

of anionic

the synthesis

and a variety

of saturated

tetra-n-butyl

and Travers

have

and reactivity

CaZn(nkBu)4

reported

anionic

zinc,

of the dodecahydro-nido-decaborate(2-)

[7].

complexes

which

obtained

by ionization

2 ZnB10H12-2

yields

reaction

a compound

2CH3ZnI

isolated

+

3NaH

in water

results

Et20

of the neutral

is a bis-ether

%%

of methylzinc

+

ion

salts

compound

are

which

readily according

complex:

ZnZf

+

iodide

of the composition

cadmium

as the bis-(trimethyl-

or the bis-(methyltriphenylphosphonium)

to new analytical

The

were

to-

[61. _

complexes

ammonium)

or

and o, @-mnsatu-

and mercury Th e zinc

alkylzinc

appeared.

of calciumzinc

Greenwood

Bi’

with the synthesis

investigated

tetrachloride

Me

Zn(B10H12)‘-

with

sodium

NaZn2(GH3)2%

NaZn2(C’H3)2H3

f

+

hydride for

4 Et20

in THF

which

the

2NaI

(11) following

structures

were

considered

kj

_. H “3-Z++,

‘‘;r n-C%

H

: I_.*. .

ZINC

81

J

Reductions with

with this

reductions

LiAlH4,

precursor high

hydride

converts

NaZnH3

The and

Beach

has

NaZnE$:

zinc

or

THF

4KH

2KZn(sec-Bu)3

diethylether

diethylether reaction

Referencesp. 112

of potassium

2

+

to

f

stability

than

been

hydride

(II) is a

heating

(CI-$),Zn

has

%nH2 I8 _ -‘.

obtained

with

under

xTHF

by Ashby

di-sec.butylzinc

of the anionic

K2ZnH4

-

the

is

quite

reaction

complex

2 KZn(sec-Bu)3

+

Zn

thermally

of zinc

as a route

of the thermal energy

+

K,ZnH4

unsuitable

an activation p 11.

-

K2ZnH4

found

at -45-50° study

Zn

3 l5

ZnH2

authors

a kinetic

thermal

K2ZnH4

facile.

Moderate

+

obtained

[S ,: _ i

-I- 3 (see-Bu)

Russian

of zinc.

and by the hydrogenation

in THF

In contrast

greater

to those

particularly

NaZnH3

hydride

by the reaction

KZn(sec-Bu)3

this

(II) into

somewhat

quaternary

in benzene

From

hydride

4

similar

being

ternary

THF

N~Zn(C~),~.x

results

of nitriles

to the first

vacuum

afford

of 27.9

Kcal/mole

6 C4H10

stable

iodide

to zinc

decomposition

+

with

hydride of-zinc was

[9j.

LiAlH4

in

$Oj_ hydride

obtained

in for

82

J-G_ NOLTE$

II.

REACTIONS

A.

Reformatsky The

remained

this

research,

past

reaction

year

of functionally

which

has

new

and related aspects

have

perature

in benzene

observed

that

vent

procedure

containing

8-hydroxy

allows

conditions,

e.g.

dilute HCl

BrZnC%C

Ph\

Stereo-

Rathke

at room

yields

may

be obtained

when the carbonyl l2 13

o-bromoesters of

The

and,

compound

/ \

of this

is’especially

. of alkyl

8-hydroxyacids. under

o-

The primary

extremely

mild

-0 OSi Me3

C(OH)C%COOH

carbaethoxymethyl

reaction group

has

(80%)

been

applied

in organosilicon

more

when a sol-

advantage

instead

hydrolyzed

tem-

and Lindert

temperature

is used,

synthesis

at reflux

Et/

The Reformatsky of the

In the

:r 3]: i.

+

_

In

chemists,

in the literature.

conducted

condensation

0 Ph-&-Et

of French

emphasized.

solvents.

trimethylborate

are

research.

attention.

readily

esters

reagents

of the Reformatsky

is normally

quantitative

a facile

trimethylsilyl

are

appeared

received

of trimethylsilyl

dbromoesters

the domain

applications

proceeds

apparent

organozinc

of organozinc

aspects

have

to base-catalyzed

The use

largely

synthetic

also

area

or benzene-ether

reaction

is most

susceptible

been

reaction

that nearly

mixture

active

reactions

The Reformatsky

important,

most

reactions substituted

than organometallic

numerous

chemical

COMPOUNDS

and related

the single

rather

reaction

ORGANOZINC

sllemistry

has

organic

OF

for

the introduction

k4],

organogerma-

..

ZINC

83

c-*

niUm

151 and

'?MX

organotin

+

E.g.

is used

compounds:

3

ZnBrCH2COOEt

Nitrones furan

$4

maybe

--+

appliedas

as the solvent

carbonyl

and

+

analogs

ZnBrX

whentetrahydro-

the reaction

temperature

react

zinc and

N-methyl-C-arylaldonitrones

to yield the corresponding

$MCH;?COOEt

with

is controlled, o-bromoesters

2-methyl-3-aryl-5-isoxazolidones

(III) '>6-: _ 2

\c//p \ /I

i

OEt

jN\ Me

OZnBr

/--

>

kjLc_&;, /

-BrZnOEt

\ c=o

MeANlO/ (III)

Several sation

reactions Luche

reaction nearly

studies

and

have

with

dealt with

Reformatsky

Kagan

have

with Schiff bases. quantitative

formation

(IV). At refluxtemperature formed

as well.

degree

of.reversibility

References p. 112

The

investigated The

the stereochemistry

preformed

of aminoesters

were

of conden-

reagents.

a certain

results

stereochemicalaspects

amount

reagents with

at -18O

react

with

erythro-configuration

ofthreo-isomer

interpretedinterms

for the condensation

of the

reaction

(V) is

of a certain . 17 :

11

.c

LG. NOLT+:-

84 ZnBr

I;I I ’

7

Phb&N-Ph

0

RCH-C” +.

I R----C-GOOR’

PhCH=N-Ph

-COOR’

A

H

I;.

(VI

(IV)

A_ stud?

of the stereochemistry

to Z-methylequatorial the order

ZnBr

1 Ph&-A--Ph

‘OR’

+ +-

I Rrr,&

sf

I

nBr

of addition

and 2-ethylcyclohexanone attack

the ratio

of 4jl

revealed

of Reformatsky a strong

to cis-epimeric

of -trans-

reagents

preference

alcohols

for

being

in

E8]:

f

.aR

0

BrZnCEI2C~

‘OR’

CL

w

, OH tE$COORl

This

is the trend

type

of addition

generally

coworkers

product

a .

threo-

compounds

H

* *

s

H

erythro-

derived

rapidly

(650/d isomers

-6

11.

that in DMSO

reagent

Ph

Ph--6-A--COOMe BrZnO

shown

and benzaldehyde

(35%).and

H

have

of the Reformatski

-bromophenylacetate of erythro-

by alkylzinc

for

this

(AS 69; 2231.

Blagoev-and densation

followed

from

equilibrates

$9j:

H

.

, I

Ph--C-C-COOMe Bri%O

at 45O the con-

A Ph A

threo-

methyl

o-

to a mixture

ZINC

The

85

same

authors

ary butylgroup (erythro/threo DMSO

that

observed

slightly favors the formation = 48/52)

at -5Othe

bi].

condensation

the Reformatsky

of the methyl

replacement

Gaudemar

of the erythro-isomer

et al. have shownthatin

of benzaldehyde

reagent derived from

by aterti-

or acetophenone

ethyl or propyl

with

o-bromobutyrate

is kinetically controlled [21]. The asymmetric reagents

has

been

realized

tion in an asymmetric mine) has made

synthesis of 8-hydroxyesters by carrying

which

Reformatsky

possible the synthesis of p-hydroxyester

reagent

as high as 98%.

was

dia-

with (S) con-

Application of the

in dimethoxymethaneincreasedthe

on the substituentgroups

depending

condensa-

solvent. The use of (-)spartein (a tertiary

figuration having optical purities preformed

out the

using achiral

opticalpur ity

in the order

of 35-98s

t22j. Reformatsky

reagents

undergo

with diethyl alkylidene malonates, yields of 52&O%

conjugate addition upon interaction 1,4-adducts

having beenisolatedin

k3]:

/ EtooCC?R’ CH---CH R'

A similar

1,4_additiontakes

allowing the preparation

Referencesp. 112

\

COOEt

COOEt

place with alkylidene cyanoacetates

in 50-60 yield of o-cyanoglutaric

esters

;241:

J.G. NOLTES

86

CH H R

\ /

CN

/

c=c

C

\

0

//

BrZnCH2C

\

COOEX

R--CH--CH IqzJ-+

1

halogen

bonds.

derived

from

C~-eooEt

been

undergo

A complete

reported

developed

reagents

ethyl

-.

‘Cody

Ol3

(R= Et, n-Pr,

Reformatsky

product

coupling study

o-bromobutyrate

and conditions

reactions

with

of the reaction

obtaining

(VI)

-.

i-Pr)

carbon

of the reagent

with bis(chloromethyl)ether

for

.’ :-. :

/

in 5545%

has

yield

were

p51:

2

K1=y20

The

synthesis

I?-60%

has

been

matsky

reagents

of esters effected

with

of substituted

by Russian

a-ketoesters

( EtOe+G%-!20

(r,ou

malic

workers

acids

via

in yields

condensation

of of Refor-

$26 :

1

0 Ph:COOR

+

BrZnCHR’COOR

PhC(OH)(COOR)CHR’COOR W (R=Me,

Several substituted matsky

papers organozinc

reagents Methyl

undergoes

have

dealing

compounds

synthetic differing

applications from

R’=H,

Me, Et)

of functionally

the traditional

Refor-

appeared.

Q’-bromocrotonate

conjugate

with

Et;

addition

affords

an organozinc

with diethyl

alkylidene

reagent malonates.

which A mix-

..

87

ZINC ture

of the products

ment)

(VII;

straight

addition)

and

(VIII;

allylic

rearrang-

is isolated

COOEt R-CH=C

/ \

+

BrZnCl-$-CH=CH~OOMe

COOEX

R-CH-CH(COOEt)2 7qF

R--CH-CH(COOEt)2

kH+H=CH--COOMe

I

+

CH2=CH-CH400Me

(VII)

(VIII) fR=Et,

Diethyl upon

dibromomalonate

condensation

hitherto

with

reported

R-CYo

affords

aldehydes

n-Pr,

an organozinc

affords

in yields

BrZnCBr(COOEt)2

(H20)

‘H

of the intermediate

in dimethoxymethane

results

condensation

reagent up to

.

52%

which not

R-CH(OH)-CBr(COOEt)2 (R=Me,

Reaction

and Ph)

28 : Cl

a-bromo-8-hydroxydiesters

+

i-Pr

product

in the formation

Et, n-Pr,

with

CC 5

acetyl

and n-Hex)

chloride

of the methoxymethyl

derivatives:

R-CH(OZnBr)--CBr(COOEt)2

Reaction

with

acetates

28 : 111

References p. 1 i2

acetyl

chloride

MeCOGl CI-$(OMe)2

in diethylether

R-CH-C

affords

Br(COOEt)2

the corresponding

J.G. NOLTES.: _-

88 MeCOCl.

R-CH-CBr(COOEt)~

R-CH-C

>

I

OZnBr

The

same

vz”

organozinc

malonates

reagent

with formatiou

below

-65O

may

esters

(IX;

yield

RCH=C

of &

be hydrolyzed 62%

for

COOEt :-

/ \

readily

‘,. ..

with diethyl

which

alkylidene-

if the temperature

to the corresponding

R=Me)

f

reacts

adduct

Br(COOEt)2

I OCOMe

is kept

o-bromotetra-

E9-j:

\

Br ZnC Br (COOEt)2

(30)

COOEt

/

RCH ’

CH(COOEt)2 C l?&OOEt)2

(IX)

At higher

temperatures

cyclization (X;

with formation

yield

59%

r

for

Russian coupling acyl

workers

of orgaiiozinc

chlorides

zinc

bromide

resulting

tetracarboxylic

in

.ester

psi:

ZnBr

CBr(COOEt)2

eliminates

of a cyclopropane

R=n-Pr)

R4I-L_(C*oEt)2

[I

the adduct

1

-ZnBr2 -

R--CH

’

1 have

,G(COOEt)2

prepared

reagents

derived

I C(COOEt),

o -substituted from

B-diketones

o-bromoketones

vi& the with

$01:

(R=Et, (R* =Me,

n-Pr, n-Pr,

n-Bu) n-Bu,

Ph)

ZINC

89 Various

derivedfrom Addition rated

synthetic

applications

a-bromonitriles

nature

of R and

69; 218) have

(AS

to benzalacetophenone

8-hydroxynitriles

of cyanomethylzinc

leads

reagents

been

reported

of Y, b-unsatu-

to the formation

(XII)

(XI) or of 64cetonitriles

@l].

depending

on the

RI:

OH PhCH=CH--&-CRR'CN &h

9

+

(XI)

PhCH=CHCPh 0-p

R’

Ph\,

i

5:

CHCH2CPh

NCCRR'

(XII)

Reaction

with

crotonaldehyde

results

R’ MeCH=CH-C/' 'H

With

diethyi alkylidene

the corresponding of 55-70s

R'

c---cN

only:

9" MeCH=CXH---CRR'CN

_ (30)

R'

malonates

diester

1,2-addition

ZnBr

\I

+

in

.exclusively

(XIII)

nitriles

having

l,&additiontakes been

isolated

place, in yields

bl]:

ZnBr \/ _C-CN

,coom f

R'UH--CH(COOEt)2

R"CH=C

R'

I 'COOEt

R--C-R'

i

a

CN

,

(XIII)

Preformed

organozinc

(AS 67; 237)addacross formation

the

reagents C=N

derivedfrom

double

in good yield of 8-aminoamides

References p. 112

bond

o-bromoamides

ofschiffbases

32 : Cl

with

I.G. NOLIE&

90 ZnBr RCH=NR'

R'KH-CONE~

i

'CH--CH(R")--CONE$

__3

@-!Z”) The

reaction

85115

B.

proceeds

of alkylzinc

-carbonand The wards

and

alkenylzinc

carbon-hetero

chemical

of such

ular of French valuable

chemists.

synthetic

Jones

and

-phenylbutanal Grignard

reagents.

istry for zinc and

prepared

four-centre

compounds

of alkyland

with carbon-

andthe

alkenylzinc

mechanistic

have

continued

This

researchhas

compounds

and

to-

stereochemical

to attract attention in particproduced

comparedthe

stereochemistry

dimethylcadmiumtowards

and

change in metal,

R"=Et).

anumber

of

procedures.

eta&have

dimethylzinc

and

:

(e.g.

atomunsaturatedbonds

reactivity

reactions

:.

R'NH'

of stereoselectivity

if R=R'=Ph

unsaturatedmolecules

aspects

Me;?Gd

with a high degree

ratio of diastereoisoners

Reactions

:

R

I

2-phenylpropanal,

2-phenyl-3-methylbutanalThe

observedtrendin of halide

the absence cadmium

from

transition

reactions,

MeLi

are

state (XIV)

of the addition

of

2-

withthatobservedfor stereoselectivity

dependence

on

the stereochem-

and the inertness

considered

with a

consistent

of with

Me2Zn

and

a bridged

p3j.

(XIV) The same

authors

chemistry

of the reaction

have

compared

the product

of in situn-propylzinc

composition and

and stereo-

icadmium

,.

reagents

_-<

ZINC

with

91

4-tert-butylcyclohexanone.

shows Cd

preference

reagents

give

two instances product

for

The

reduction

over

preferentially

gave

zinc

reagent

addition.

axial

Whereas

both

the

Zn reagents

reduction,

the non-thermodynamic

1’Zn-PrMgBr-ZnBr2”

axial

alcohol

Mg -and in

as the major

@I:

exn_pr&yH 3 1%

0

“2n-PrMgBr;

20%

ZnBr2” >

The

addition

accelerating of

of tetrabutylammonium

effect

di-n-propylzinc

tion

reaction

butanol-1 results

after

(from

complexation

the carbonyl

The reaction

resulting

a pronounced

/benzylalcohol

than with

of 9 for

and benzaldehyde

causing

indicate

pentene-2

(by a factor

and little

>I)

for

has

on the addition influence

Bu4NCl).

an

reaction

on the

reduc-

ratio

l-phenyl-

Spectroscopic

with the dialkylzinc

rather

35 . Cl

of the organozinc

in the formation

salt

(Cl>Br

in the product

to 15.6

of the

proceeds

Bu NCl) 4

change

1.3

compound

with ketones

halides

reagent

with partial

of a mixture

derived

from

allylic

of linear

l-bromo-

rearrangment

and branched

alcohols

hydrolysis:

OZnBr Et--CH=CH-C~ZnBr

f

RR’%=0

+

Et--CH=CI-GC

I

--CRR’ ‘Hz

Et

I

CI-$=ClGCH-CRR’

iReferencesp. 112

.

+

OZnBr

I

92 The

reaction

condensation

elevated

reaction

composition

been

shown

to be reversible.

and longer

temperatures

becomes.thermodynarnically

of the

thesis

has

more

stable linear

EtCH~CHC~C(OH)RR'

reaction controlled

alcohols

similar

situation applies

reagent

derived

from

applying-.

the product

enabling

the syn-

in 100%

for the condensation

l-brdmopentadiene-2,4

_-_. -;-'. '-

‘-r----

:‘..

.,.

of the type

(R=R'=Et,i-Pr,n-Bu)

A

times

By

purity

:.Y

F6-J.

of the organozinc

with aldehydes

and

ketones:

C(OH)RR'

I Cl+=CH-CH-CH=CH2

CH2=CH-CH=CH2CI$ZnBr

.

>

-I-

+

0-p)

RR’C==O

CH2=CH-CH=CH--CH2,(OH)RR' (XV)

Changing

reaction

plus 45 hrs linear

conditions

at 60°/THF

dienic alcohols.of Allylzinc

cyanoacetates

bromide

from

allows type

3 hrs

at 20°/THFto

the exclusive (XV)

undergoes

synthesis

3 hrs

at 20°

of a variety

of

ET]. conjugate

addition

with alkylidene

24: Cl

CH2=CHCH2ZnBr

-I-RCH=C

HCN WC%

‘coozt

(R=Me,Et,n-Pr,i-Pr,Ph)

Reaction

with

substituted

the ethoxymethylene

product

(XVII)

in 20%

compound yield

24 : L-l

(XVI) yields

the bis-ally1

I

ZINC

93

CI12=CHCH2ZnBr

.CN EtOCH=G’

’

CI12=CH-GH2, 3

place

(XVII)

conjugate

addition

upon interaction

in either

toluene

H

/

“=c

\

H

or

of THF

(AS

69;

224)

di-n-butylzinc

and carbonyl with

methyl

Cl +

B

“z

Zn

to produce

a-chloroacrylate

(XVIII)

COOMe

\ /

/

c=c

that the

reaction

conjugate with

addition

a second

the cyclopropane

product

molecule

(XIX)

with

Cl OZnBu

‘C’ / a

Me0

cyclization

take

AMe

H

shown

addition

38: L-1

H

It was

\COOEt

cy=cI&cq

COOEt

(XVI)

Both

,cN

CH--CH

Bu

(XVILI)

of methyl

elimination

undergoes

a

o-chloroacrylate

of n-butylzinc

chloride:

H (XVIII)

+ H’

‘C=C

/

Cl *

‘COOMe

/Cl

=I+<. \C/

GOOMe

+-

BuZnCl

/\

c5HiI

kCOOMe

(XIX)

n- Butyl(dimethy1 dition

38 . [:I

Refen?scesp_ 112

malonato)zinc

exclusively

undergoes

conjugate

ad-

J.G. NOL*:.

94

Three-membered ethylzinc NMR

chloride

ring

formation

with methyl

the product

of this

reaction

is

H

\ /

/

c=c

\

As

cis-dimethyl

(XXI).

upon interaction shown

of

.~

by IR and

1-propyl-2-chloro-

The following

reaction

scheme

.

consider.ed

H

occurs

c-chloroacrylate.

-1,2-cyclopropanedicarboxylate was

also

1391:

Cl f

EtZnCl

<

n-Pr--_C.

6 YFO

COOMe

0 ZnCl

&Me

(XX)

H

(XX)

-IH

\ /

c=c

/ \

Cl

:

ZnCl

COOMe OMe

COOMe

(-ZnC$)

>

n-Pr

-

COOMe

k4 =?z

Cl

(XXI)

The allylic

reaction

of allylzinc

rearrangment,

e.g.

reagents

with

cx-alkoxyketones

involves

40- : Cl

G2%CH=CHCH2ZnBr

C~=CK-CH(C2H5)-~C3~)(OH)-CErZOCIK

.-.

95

ZINC

o-Alkoxyesters yield. upon

afford

Pentenylzinc reaction

r

observed

reagent

with

alkoxycarbinols

diallyl-substituted

ethyl

affords

a

3/l

mixture

of (XXII)

the formation

ethoxyacetate;

in excellent and (XXIII)

of (XXIV)

is not

..

40 i .

-2

C~=CH-CH(CZHS), ,

CH(OH)C%OC&

(XXII)

C%=CH-CH(C&

CJ+=CH--CH(C&

\ ,

CZHSCH=CH-C~

CH(OH)C~OCzHg

(XXIII)

C&.CH=CH-C~, CH(OH)CI$OC2Hg

CZHSCH=CH-CH/

The

formation

reaction

of diallyl-substituted

of imino

the intermediate gested,

via

ethers formation

an isonitrile

PhNH=CHOEt

+

?

PhN=CHR

The

reaction

to otherwise amines

with

allylzinc

+

with

bromide base

Rg)

organozinc

available

RNHCRr3,

amines

e.g.

the

proceeds

as previously

via sug-

.-> -MOR

(I-$0)

PhNHCH3

compounds

symmetrically kg:

from

probably

and not,

P&N-CH-R

Y Ph-N-CH(

of isonitriles

of the type

Referencesp. 112

RM -

difficultly

secondary

of a Schiff _ . L4lj:

RM

(XXIV)

offers

substituted

a route secondary

J.G. NOLTES 1:.

96

Ph--N=C:

+

THF w

3 CH2=CHCH2ZnBr

PhNHC(C%CH=C%)3

;1

0-p (30%)

Such

compounds

reaction

may

of allylzinc

be obtained bromide

(OEt),

Ph-N=C

attractive

yields

via the

@2j:

with iminocarbonates

RM

f

in more

“: yEt

__,

Ph-&-C(R)OEt

/

6MOD)’

PIrN=C(R)OEt

+

RM

9

.

Ph-I++ (-MOEt)

PhN=CR,

Y

+

-

(RM

With

substituted

rearrangment

allylzinc stops

reagents

=

PhNHGR,

CH2=CHCH2ZnBr;

the reaction

at the iminoether

stage

which

yield

involves

61%)

allylic

@q:

,OEt PhN=C(OEt)2

Nivert

+

RCH=CHCH2ZnBr

and Miginiac

derived

from

affords

a mixture

former

strongly

have

propargylbrornide

shown

CH2=C=CHZnBr

PhN=C, (R=Me;

66%)

(R=Et;

40 ‘$11

that the organozinc

with gem-aminoethers

of the acetylenic predominate

___3 (%O)

and allenic

amines

CHRCH=C%

reagent

or with aldimines in which

the

[4g : KC= CC%CH(R)N(C,%)2

+

iV@

C4h$OCH(R)N(C

zH5)2

CI-$=C=CHCH(R)N(C,H$2

. ..I : :._.

ZINC

97

CH2=C=CHZnBr

HC= CCH2CH(C&NHR

-I-

-IF

CbHSCH=NR

An independent bases

was

tained

mixtures

obtained vation

of the reaction by Moreau

in yields

with

and secondary

of the ring occurs Whereas carbon

atom,

alifatic

carbon

H4

of

inversion

the

Ph.

et al.

opening

with

=.c-_y ‘0’

!I R, 2R)

Referencesp. 112

reagent

yield

amines

43j. c

have

:H \Me trans

as well

or with

exclusively

the highly

1-phenyl-1,2-epoxypropane

(1 S, 2 R) cis-isomer

atom

nearly

reacts

ob-

having

been

reagent

obser-

derived

aldimines

affords

reactions

of

cr-allenic

stereospecific

nature

by diallylzinc

at the benzylic reacts

also

the interesting

the corresponding

established

of configuration

the latter

made

with Schiff

authors

of the organozinc

amines,

(1 R, 2 R)trans-epoxide the

L. Miginiac

bromide

These

amines

gem-aminoethers

acetylenic

l-bromo-butyne-2

Abenhaim

44j.

the condensation

exclusively

tertiary

and allenic

up to 54%

whereas

of allenylzinc

and Gaudemar.

of acetylenic

3-bromobutyne-1

nearly the

study

reported

that

from

CH2=C=CHCH(C&)NHR

exclusively to a small

carbon

which

atom.

at the benzylic extent

at the

E5]:

Al12Zn

cyo) 3-phenylhexene-4-ol-

I(2 R, 2 S)

zmc

99 _j,

CF$=CHC~

\

MgBr

/

c=c

Ph /-

YznBr

(30) i C~=CHC~

\ Ph

/

(22%)

C=C%

C%=CHCH2ZnBr PhC=CMgBr (65%)

‘y-%3

e$_a T

C%CH=CH2 l/2

CIY-$CH=C%

.ZnBr

I 3

Ph-C-C~MgBr

\ I

With place

vinylic at 35O,

organometallic e.g.

C33CH=CHMgBr

reagents

an exothermal

.&lBr

addition

takes

@6]:

t

C%=CHCH2Zn&

c3H7, CH-CH CH2=CHCy/,

/

\

ZnBr

Mg Br

(~0) I CH2=CHC~~~(~~!)~3~7 (58%)

Referencesp. 3 I2

J_G_NOL~“‘-.;

100 C.

Carbenoid The

continued in organic The has

reactions

of organozinc

carbenoidreactivity

to attract attention and further and

organometallic

synthesis

sub.ject of carbenoid

reagents

of their

examples been

application

area

pi'].

have

dealt with synthetic

Simmons-Smith

reagent

Gem-dimethylcycloheptadienes

compounds

on the author's

applications

zinc-copper

have

of 5,5-dimethyl-Z-cyclohexanol

OWII

couple/methylene

beenpreparedvia

coupled

of the

coniodide.

cyclopropanation

with homoallylic

ring expansion

48': Ll

Zn-Cu

L480JoHBr 2.KOH/EtOH

GH21z

The

Simmons-Smith

selective

The

route

corresponding

stereoselective -bicycle

b.l.O]d

:. :

published.

of halomethylzinc

with emphasis

has

:

in this

Severalp'apers ventional

organozinc

have

reactions

beenbrieflyreviewedbyseyferth

contributions

-_ _. '.

compounds

of appropriate

-.

reaction

of cycloocten-

to anti-bi-cycle

reaction route

-1 6.l.O~nonan c

-2-01

of cis-cyclononen-3-01

(less than 0.05%

ecan-Z-01

3-01

(XXVI)

of E-epimer

i50]:

afforded (XXV)

a stereoc49]:

affords

ahighly

formed)

to anti-

101

ZINC

OH

OH

Le Perchec

and Conia

obtained bicyclopropylidene

of vinylidenecyclopropane

Templeton

Fg:

and Wie have investigated

(3o- and 3@-hydroxy, 5,6-unsaturated

the effect of IS-oxygen functions

3o- and 3S-acetoxy,

3-ethylene

acetal) of

steroids on the addition of the Simmons-Smith

to the steroidal 5,6-double bond. studied, only

via cyclopropanation

in the presence

take place with timation

Of the various

of the

3o-hydroxy

of the expected

5-cholestene

reagent derivatives

function did reaction

3cr-hydroq-5,6

a-cyclopropano-

-5o-cholestanc

Furukawa

et al. have continued

iodoalkane/diethylzinc authors

(AS 69;

Referencesp.112

225).

their investigation of the gem-di-

cyclopropanation

reagent discovered

by these

J.G.NOLTES t

102 The reagent

relative

reactivity from

generated

decrease

diethyloinc

in the order

hexene>hept-1-ene with alkyivinylethers

styrenes

(p-value

RZnCH$

(XXVII)

carbene

(ROCH=CI$)

The

effects,

the

R--in

methylene

iodide

outcome

1s - a more

same

group

/diethylzinc

tance

has

of steric in addition

of experiments suggests

nucleophilic

The

studied

with substituted

that methylene

in reactions much

of the

PhCH$-EsZn

I

carbenoid

transfer

reactionthanthat

the stereoselectivity

= 6.6 for the same

zinc carbenoid

lithium

to

by

of dichloro-

(XXVIII)

with cyclohexene

of coordination

0

Experiments

.,__,‘~~

by the phenylcarbenoidis

(syn/anti --

to

$4.

reagent

for the reaction

found

>trimethylethylene>cyclo-

(XXVII)

The

was

and&-alkenylethylethers

importance

of -1.61+0.05)

(XXVIII)

the zinc carbenoid

of decreasingnucleophilicity).

revealed

electronic

and

tetramethylethylene

(order

(RCH=CHOC&)

of olefins towards

shows 541. c

with olefins. higher

of the benzaliodide/

Thee-selectivity

in ethers

(e.g. c/anti

in diethylether)

reaction solvent

in pentane)

to the metal

shown = 17.1

than in hydrocarbons indicating atom

the impor-

c541:

>

larger=-selectivitythanthe

corresponding

103

ZINC

Interestingly

reagent

E5Zn/CI-$+2 where

the cyclopropanation

air was

is greatly

passed

shorter

yields with

as compared

atmosphere

formation

diethylzinc

experiments

-t

dominating

are

much

anitrogen

type

cyclohexene.

authors

of reaction

intermediate

These

or

route

to

d?splays and

(42%)

of EtZnCCb PhHgCC$)

and

is postulated

E-selective

as

behaviour

7-bromonorcarane

pre-

E6].

observed

reactions

vH

for the bromocyclo-

derivative

in their investigation

dichloropropylzinc

by elimination

References p. 112

of

of the fluorocyclopropane,

CHBr21

7-chloro-

of the interaction

the formation

as well

carbontetrachloride

rormation

(via PrHgCC$

and

their z-isomers

1-chloropropene with

synthetic

and/or

the preparation

zinc with polychloromethanes and

a novel

m

+

of 7-fluoro-,

over

Russian

pene

times

at a

of zinc by the interaction

A dihalogenomethylzinc

This

the endo-isomers

mediate

reaction

performedunder

offers

CHXYI

the mostusefulfor

derivative.

reaction

and

mixture

derivatives:

E5Zn

-I-

an intermediate.

(41%)

In experiments

the reaction

improved

for the chlorocyclopropane

propane

above

with trihalogenomethanes

I

was

CHCSI

by oxygen.

of halogenocarbenoids

halogenocyclopropane

CHF21

are

of olefins by the

[55j.

The

0

accelerated

into the space

rate of 10 ml/minthe

reaction

believed

carbenoid. into the

Zn-C

derivatives

isomerization

of ethyl chloride

as dichloronorcarane,

was.carried were

of dietbyl-

if the

out in the presence to proceed

Insertion bond which

of

via the inter-

of dichlorocarbene

of EsZn yield

affords

l-chloropror- 7 of ethylchlorocarbene i571: ._ -:

J.G. NOLTES

104

Seyferth

and Andrews

of halomethyl

derivatives

iodomethylzinc

iodide metal

appropriate

-t

These

works

best

iodomethyl nitrile.

may

derivative

involve

paper

a two-step

(AS 65;

n-Bu$iH

46)

n-B

Y

Furukawa and organotin

ethylidene

38

et al. hydrides

(cf.

3

metal

prepared

bromide

SiCHI

from

by the

and of the in aceto-

of the

bond in organosilanes

or reduction-alkylation

The

exclusive

the reaction

of IC%ZnI

formation

of a mixture

shows

of

of E

that the direct

s

SiD

insertion

58 . c1 have

investigated

with the

AS 65;

the reaction

E?Zn/RC% reacts

reagent.

with insertion

46) :

EtZZn/RCHs RzR3SiH

chloride

that interaction

ZnClI

The procedure

by the reaction

or silver

alkylation-reduction eliminated.

attack

+

bromomethyl

with the silicon-hydrogen

was

of

with the

Me,SnC%I

center.

corresponding

the possibility

of triorganosilanes group

in THF

nucleophilic

heavy

best

silver

with an excess

is operative

in a variety

are

with

reagent

E5SiCE_LLD and

process

The

synthesis

e.g.

Me$nCl

as involving

at the electrophilic

In the same

sequence

and

pictured

compounds

Simmons-Smith

halide,

of their

via the reaction

bromide

IICHZ ZnI L -

C?I-transfer.

chloromethyltin

the details

and mercury

1

THF -*

are

for

lead

of tin,

or organometallic

reagent

XC%ZnX

published

or bromomethylzinc

Zn-Cu

reactions

have

p

R1R2R3SiCyR (R=H

or Me)

of organosilicon The Si-H

bond

of a methylene

or

:

105

ZINC However,

iodide

in the reaction by the organotin

methylene

group

oftriethyltin

hydride

into the

reactivities

of substituted

noid yielded

a

and

insertion,

ethylene

-1.31

p-value

(AS 69;

both

reactions

predominates

Sn-H

over

Hammet

bond.

of -1.11 LO.03

and

methylene

suggesting

correlations towards

of the

of relative

the zinc

-1.19tO.05

insertion

a similar

of the organic

the insertion

as compared

respectively,

259)

reduction

aryldimethylsilanes

for the corresponding

mercury

hydride

carbe-

for methylene

witha

p-value

of

via bis(bromomethyl)-

transition

state (XXIX)

for

59J: C' Me

/\ cl-

I 6f Si

--------H

I’\

X-

:’

'\ 6-t' ;C+lR I \ / \ . \ z.:______:y

Z=XZn,

R=H,

Z=XZn,

R=Me,

Y=I Y=I

Me

Z=HgCI-$Br,

R=H,

Y=Br

~XXIX)

III. ORGANOZINC Several organozinc Abstracts

COMPOUNDS papers

providing

compounds of patent

AS

POLYMERIZATION

details

on the catalytic

in polymerization applications

and

reactions

patents

catalysts

pounds

of the catalytic

appeared

such

has

system

Referencesp.112

Abstracts,

presentedan

polymerizations

as brought

catalyst

components

in Chemical

Kuntz epoxide

of the

about

with

will not

excellent emphasis

by zinc-containing

di-isobutylaluminium

properties

have

describing

multi-component polymerization as one

CATALYSTS

containing

of

appeared. a variety

organozinc

system,

which

of comhave

be surveyedhere.

survey

of the mechanism

on coordinative

of

polymerizations

initiator systems

bo].

The

acetylacetonate/diethylzinc/water

J.G. NOLTES

106

was

found

zation The

to be particularly

of propylene

maximum

water

bonds

revealed

l$Al khich

groups

present

and that the vn

compound

as

shown

‘Zn

The

zinc

atom

and aluminium

may

type,

was

both

study

at a maximum

that the active

Al-O-Al

coordinated

for

and

has the cata-

R-Al

to the Al-O-Al

64:

/R

play

a major

FO,

is

A kinetic

speculated

requires

component

in (XXX)

R

It was

of

with all the metal-

components. rate

61 . CJ

when the amount

to react

polymerization

of the living

the copolymeri-

and allylgiycidylether

required

%O/F$Zn.

about

is observed

in the catalyst

acac /0.5 is

to polymer

than that

that the initial

system lyst,

is less

in bringing

epichlorohydrin

oxide,

conversion

present

-carbon

effective

a major role

role

in polymer

in epoxide chain

monomer

growth

coordination

[60]:

OCHCI$OCHC%OR

107

ZINC

-?2 =:

c

rH3

/ ,O,,

,0CHCF~OCHCX~OCHCH20R

2'zh /

Recent have

d

'. ..,??I

from

papers

clarified

several

dialkylzinc

catalyst

Et2Zn/H20

system

systems.

presence

of both

62. Cl

kinetics

The

The

Zn-0

and

of the

Zn-Et

diethylzinc/water

metric

polymerization

active

polymer

Tsuruta

active

pound:

the polymerization

the antipode

resulted

monomer

in restoration

of catalyst

-stereoselective.

If, however,

to the deactivated

catalyst,

tivitywas

regenerated

of styrene

oxide

/(-)-menthol Referencesp. 112

has

k5].

Fj. been

effected

asymmetric with

been

with

com-

poly-propylene

oxide

following

addition was

dialkylzinc asymmetric

selection

the catalyst

brought

(+)-bis(2-methyl-

but the catalyst

catalyst

by

acids

dialkylzinc

with

active

Asym-

realized

L-o-amino

of diethylzinc

the optically

The

earlier

active

the

of an optically

by the further

activity,

an active

E3]. 2

active

Addition

catalyst

discussed

69; 227) has

oxide

species

using

with

(AS

optically

63. C

of the asymmetric

deactivation

compounds

an optically

afforded

catalyst

(formation

of DL-propylene

catalyst

been

the

oxide

mixture)

as cocatalysts

et al. by using

butyl)zinc/water

leaving

dialkylzinc

alcohols

by Furukawa

monomer

is im-

activity requires

of propylene

(l/2) has

of the

oxide

in the active

of epoxides

a racemic

et al. by using

or optically about

from

catalyst

bonds

initiated by

reproducibility

of propylene

polymerization

initiator system selection

catalytic

Et2Zn;

University

polymerizations

for the polymerization of free

at Kyoto

of Furukawa

of epoxide

aspects

by the removal

proved

the group

etc.

of water nonwas

added

selec-

polymerization

system

diethylzinc/

J.G.NOLTES:.

.108

Sakata

CY, $-unsaturatedketone propylene

catalyst

-dimethylacrylophenone

Conjugate gives

of EsZn

addition

a catalyst

were

and

Tsuruta

fruitful studies

dealing

the area

of carbon EtzZn/%O unitinthe following both cases trans

at Tokyo

wit__ '-the application catalysis.

with

polycarbonate alkaline the

showing

system

bil.

hydrolysis

or

in the ring opening

is

configuration

r7 1_66J-

was

of the

specifically inverted

their in

is their

copolymerization

(EPCH)using

-reduction

1,2-cyclohexanediolformed that the

ineffective.

interest

alternate

(cis ortrans) --

LiAlH4

other

compounds

of

Th e configuration

. _

@,B-

(AS 69; 224)

of organozinc

Of particular of the

copolymer

and

were

continued

have

cis-1,2-epoxycyclohexane

(l/l) catalyst

of

stability at high temperature

University

of the stereochemistry

dioxide

acrylophenone

or methylacrylate)

activity and

of polymerization

investigation

for the polymerization

to cu,@-u&aturatedketones

with better

of diethylzinc/

but carbonylcompounds

suitable,

2-furylacroleine

(e.g.

Inoue

systems

$!I<3. Methilisopropenylketone; .. -

oxide

than ketones

the effectiveness

demonstrated

et al. have

was

a the

EPCH

determined

of the copolymer.

In

found to be exclusively

EPCH

carbon

atom

involved

during

the copolymerization

k7: LI

Et2Zn/J+0 f

Hydrolysis

nCO2

of poly-(propylene

polymerization

carbonate)

of R-(+)-propylene

oxide

obtained

by alternating

with carbon

dioxide

co-

using

a

I E%Zn&O

catalyst,

tollowed

resultedintransformation propylene

by treatment

of the epoxide

glycolbis-p-nitrobenzoate.

with p-nitrobenzyl unit of the copolymer

Determination

chloride, into

of the optical

109

ZINC

activity

of this

asymmetric fore,

ester

revealed

carbon

atom

of the epoxide

the organozinc-catalyzed

at the

methylene-oxygen Kawakemi

ring

linkage

and Tsuruta

or methyl

Methyl

in toluene,

type

catalyst

with

methyl

zation

or .THF,

68 . II

activity

n-

for

acrylate

carried

using

n-Bu;!Zn

results

studies

pj. with

or

n-butyl-

of the copolymeri-

indicate

but in HMPT

out

(HMPT)

or copolymerized

The

as kinetic

of diethylzinc system

place

as a third

allowed

methacrylate.

takes

obtained

a radical-type

an anionic

mechanism

cocatalyst

the block Under

and products

copolymerization

certain with

in a Ziegler-Natta

conditions

controlled

of ethylene no homopolymeri-

composition

could

be

[69].

The

valence

polymerize

state

propylene

relationship

or the molecular

A.

as well

mechanism

was

triamide

solution

as a catallyst.

predominantly

of methyl

the polymerization

or HMPT

in toluene

The use

served

catalytic

There-

38 . Cl

applies

direct

place

an anionic

can be polymerized THF

experiments

polymerization

takes

a low

of the

copolymerization.

or hexamethylphosphoric

(dimethylmalonato)zinc zation

indicating

provided

o-chloroacrylate

styrene

opening

configuration

in the polymerization

methacrylate

in dimethylsulfoxide

of the

upon

observed

-butyl(dimethylmalonato)zinc

IV.

the inversion

of titanium

in the

to isotactic

between weight

the

EsZn/TiC13

polymer Ti

2f

or isatacticities

has

content

been

and the

catalyst

used

investigated. catalyst

of the polymers

was

A

activity not ob-

70 . Cl

STRUCTURAL,

Structural An X-ray

Referencesp. 112

SPECTROSCOPIC

AND

PHYSICAL

STUDIES

studies crystal

structure

determination

of the anionic

zinc..-

to

J.G. NOLTES

110 -borane

complex

-decarborato)zincate The

structure

ligands

kSMeP]2

can be considered

Fig. 1. Structure boron

(Af, 1971,

The

only cfrom

been

reported

two bidentate

to zinc (Fig-

EloHlzZ-

1).

s h owing

N.N.Greenwood

[7q.

the positions

etal.,

of the

J.Chem.Soc.

Skj.

studies

IR and

Raman

spectra

methylzincate

7L$Zn(C3)4,

reported.

spectra

2n-C

has

to comprise

of i;'~MeI$~n(B10H12)2]

atoms

B. Spectroscopic

band

kn(BloH12)d

co-ordinatedtetrahedrally

zinc and

bis(dodecahydro-nido-.

methyltriphenylphosphonium

The

at 520 cm

-1

stretching

of the isotopic

6 L5Zn(CH-$+

indicate

Td

in the IR spectrum mode

bill.

symmetry

analogs

and

of lithiumtetra-

7L$Zn(Cnj)4

around

of 'Li2Zn(CD,),

the zinc

been

have atom.

isassigned

A

to the

111

ZINC A iodide

PMR in THF

solution

alkyl exchange PMRtime

(corresponding

to the

Oliver

et al. have

of

ZnI2

in going

of

borate(2-1 Travers

the

anionic

ion

groups

and

for changes

kinetic

solvent

equi-

AS

28.87

*

MHz

on the rate and dimethylzincparameters

are of the

(dichloromethane,

solvent

eu) to a strongly

(diethylether,

coordinating

solvent

= + 2 eu). and

80.53

MHz

llB-NMR

of the dodecahydro-nido-deca-

complex

were

of zinc iodide)

in the mechanism

coordinating

has

~e4Nj2[Zn(BloH12)21

[7] and the results

on the

1.00/1.05

the Schlenk

in the system

energies

of the

zinc

amount

effects of solvent

a non-coordinating

discussion

is slow

(R=Me,Et)

the

AS #= z-14

173j. At -70°

ratio was

that

ethylzinc

500 at -9OO):

Ea f' = 16.3 kcal/mole;

A detailed spectra

studied

to a "weakly"

(triethylamine,

Zn/i

with a small

2RZnI

is presented

9 ..1 kcal/mole.

the

and

et al.

diaikylzinc

confirming

Activation

from

and

in which

of methyl

.- ? p41.

< 5 kcal/mole)

Ea '=

0

for methyl-

by Evans

iodide

right (K>

exchange

Evidence

reaction

reported

observedat-90°

+

trimethylindium

Ea

solutions

52Zn

reported.

been

to "alkylzinc.iodide"

line was

mechanism

equilibrium

alkylzinc

For

lies well

librium

has

between

scale.

only one

of the Schlenk

study

been

correlated

presented with

by Greenwood

the known

and

structure

L711 in the solid state. t-Butoxy in

radicals

the presence

tion at the cavity t-BuO=

metal

of diethylzinc centre.

the E.S.R. +

Et2Zn

Referencesp.112

generated

induce

of di-t-butyl.peroxide

an homolytic

If the reaction

spectrum -+

by photolysis

is carried

bimolecular.

out in an E.S.R.

of the ethyl radicaicanbe EtZnO-t-Bu

-I- Et.

substitu-

observed

75 : [I

J.G.EiOLTEs..’ :

112

C.

Other

physical

Complex with

studies

formation

2,2’-bipyridine,

ethylene

ethylene

diamine

stoechiometry

(CH_&Zn,

of

has

been

diamine

studied

and dissociation

agreement

with earlier

(C21-I$2Zn and

(iso-C3I-&-Zn

N,N,N*,N’-tetramethyl-

by an oscillometric

constant

results

and

method.

of the complexes

(AS 67; 235)

The

were

in

fi61. -3

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