Stereochemical and mechanistic aspects of the nickel complex catalysed formation of olefins from allylic alcohols and Grignard reagents

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Tetrahedron Letters Vol. 22, pp 1157 - 1160 @Pergamon Press Ltd. 1981. Printed in Great Britain

STEREOCHEMICAL COMPLEX

AND

MECHANISTIC

CATALYSED

FORMATION

ALCOHOLS

Hugh Institut

Felkin

de

GRIGNARD

and

Monique

des

OF THE

OF OLEFINS

AND

Chimie

91190

ASPECTS

FROM

NICKEL

ALLYLIC

REAGENTS

Joly-Goudket

Substances

Gif-sur-Yvette,

Naturelles, France.

and Stephen The

Dyson

Perrins

G. Davies

Laboratory,

Oxford.

OX1

South

3QY.

Parks

Road.

England.

The reaction of (+I-S-but-I-en-3-01 with phenylmagnesium Abstract: bromide in the presence of bisCtriphenylphosphine)nickel dichloride has been shown to proceed with inversion of configuration to yield C-)-R-3-phenylbut-I-ene.

We have Grignard

previously

reagents

shown

(i.e.

alkyl

or aryl

of Grignard

and we

that

report

here

of configuration

In with

PhMgBr

to give

together

with

of

bear

the

another bearing

nickel

a labile

mechanism

for

feature

B-hydrogen),

the

is illustrated

the

alcohols

substitution

exclusively

complex

of olefins

of allylic

catalyst,

alcohols proceeds

for

carbon

a mixture

alcohol

the

ally1

evidence

presence

proposed

reaction

at the

the

do not

The

with

the

that

reaction

dichloride

occurs.'

reagents

demonstrated

in the

those

bisCtriphenylphosphine)nickel by

that

of this

hydroxyl

3, 4 and 2 --

1.

in the

namely

racemic

already intermediates2

that

ratio

44

but-I-en-3-01

:

Ph

-

+l

‘Ph+

reaction

inversion

occurs.

PhMgBr

1

of

function

catalysed

We have

-6.2

Ph

presence

Cn3-allyl)nickel

mechanism,

1,

non-reducing

hydroxyl

complex

in figure

function

(Ph3P)zNiClz

in the

of the

nickel

through

with

Ph+OH

40

:

16

2 reacts respectively

1158

L2NiC12 2RMgX

(L,Nil

&OMgX I Ni

L’

Figure

1.

allylic

The bromide 42%

Mechanism

alcohols

reaction

of the

(9.2%.

olefins

Cal';

occurred

with

shown

the

amount

C<7%).2vrJ inversion of the reaction

of

in Et201

3, 4 and -neat)

predominant

2 are not

faster

than

racemisation

By analogy

with

of configuration

(n3-allyl)nickel (figure

2).

reagents.

was

isolated

active fast the

the

by

shows to

arises

followed

34

lead

from

phosphine).

optical (I.25

: 18.

purity)

mmole)

with

gave,

phenylmagnesium

after

16h

reflux,

C-)-R-3-Phenylbut-l-ener(-)-R-3r ~.L.c.~

the n3-nl(primary

to complete

The

reaction

than

of other from

the

alkyl)-q3

amount

transition

inversion

retention

of

alkyl)-n3

racemisation.

n3-n'(secondary

by

of olefins

has

-

therefore

of configuration.4 that

is greater

chemistry

:

94%

of 1

preparative

inversion 2

enough

clearly

complex

48

corresponding

(~75%)

mmole;

presence

ratio

formation

(L=tertiary

(12.5

in the

5 in the

(24.6%)

of optically

in figure however,

L2MiC.12 catalysed

Grignard

(+I-but-I-en-3-01

1.44M

= -1.470

Isolation

are,

of

(50 mmole;

of the

and

‘L

of

5

interconversions These

reactions

interconversions

since

of syn-anti interconversion -metal systems7the overall configuration

configuration

during

during

the

formation coupling

1159

OH

(+)-S-2 \ Ph-[ t$

Ph_( Nd l

-

(-1-R-3

Ph-[ Ni]

Ph-[‘Ni 4

T

1 ,,ICH:, “i,

d-e

-

<

-

PhiNi]

Ph-[Nil

figure and

the

2.

Formation

mechanism

of

of

(-I-R-3-phenylbut-L-ene

racemisation.

from

(+I-S-but-L-en-3-01

1160

The

alcohol

the Heck

5.

reaction

formed

in 25%

catalysed

yield,

is presumably

by palladium

produced

by a reaction

analogous

to

8

complexes.

OH

In

the

therefore fi after

formation

-6 must

of -6 the

possess

the

recrystallisation

Acknowledgments:

centre

of the

alcohol

-2 is not

same configuration as C+)-S-but-I-en-3-01. 22 Cdl D = -34.8' CC=S. CHCL3 containing 0.5%

is

We thank

asymmetric

Dr.

C. Georgoulis

(Paris)

for

a generous

involved The

and

rotation

of

EtOH).9

gift

of

C+)-S-but-I-en-3-01.

References:

1.

C. Chuit, 1977,

2. 3.

H.

H.

-127.

Felkin

For

full

and

G. Swierczewski,

Orsay,

-74,

and

G. Swierczewski.

J. Organometal

Chem..

Tetrahedron

details

see

Letters.

M. Joly-Goudket.

1972,

1433.

These

3e

Cycle.

Universit6

de

Cdl 22 D = -6.39'

has

(neat)

,

D.J.

Cram,

J. Amer.

Chem.

Sot.

1952,

2137.

A similar J.W.

Falter.

6.

Note

that

B.L.

Buckwalter.

situation

B.M. -S0c.r

and

Trost. 1977,

8.

R.F.

9.

Reported

M.E.

total

E. Wenkert

H.

G. Roussi

1972.

CR)-3-Phenylbut-I-ene

5.

7.

C. Frajerman,

experimental

Paris-Sud. 4.

Felkin.

371.

Heck.

is known Thomsen

1-R. P.M.

1649;

Act.

Chem.

2

1977. F.W.S.

Res..

Cdl D Sot..

in analogous

Mattina,

1979.

1936,

January 1981)

Chem.

-12.

and

Trost

M.L.H.

complexes:

Chem.

Sot..

ally1

nickel

1978, and

Green,

1971.

K. Naemura. -100. P.E.

93.

2642.

systems. M-F.

Salomon.

6445. Strege.

J.C.S.

Dalton,

J. Amer. 1974.

146.

CC=S. 85.

Sot..

B.M.

2615;

Benfield

= 24.7'

J. Amer.

palladium

M. Joly-Goudket,

J. Amer. -30.

ally1

for dialkylated

H.Felkin.

Wovkulich.

-99.

J. Chem.

M.J.

occurs

Burfitt,

Tetrahedron.

(Received in UK

and

equilibration

rotation:

Philips,

to hold

CHCls);

J. Kenyon.

S.M.

Partridge

and

Chem. 1324.