Stereochemistry of “no-mechanism” reactions. II. Asymmetric induction in the Claisen rearrangement.

Tetrahedron Letters No.*4, Printed in Great Britain.

STEREOCHEMISTRY ASYMMETRIC

K. Hill

Laboratory,

and Anthony

Princeton

initiated

the best-known

rearrangements,

is the Claisen

lated about the mechanism via a concerted,

It would transition

of little experimental

Alexander retained

group of thermally

to acid and base catalysis,

that a reaction

evidence.

degree

Although

which has been accumureorganization

specifically

i.e., the simultaneous

of a new asmetric

such a highly

accepted on the basis of investigators

bond

at the possibility

destruction

of

of asmetry

center b in a stereoswcific

-! ',_phenoxypentene-

3239

have

, only one previous

were able to show that some optical

in the rearrangement

ordered

of stereospecificity,

a number

of the allylic double

has been directed

and Kluiber'

with

which has been generally

in geometry

induction,

a and creation

recognized

with an electron

have an appreciable

but this is a conclusion

metric

N.J.

cyclic pz,xess:

state would

investigation

insensitive

is consistent

be anticipated

studied changes

Princeton,

1964)

All of the evidence

rearrangement.

II:

G. Edwards

of a now widely

nearly

Press Ltd.

REARRANGEMENT.

University,

27 August

Pcrgamon

REACTIONS.

IN THE CLAISEN

(Received

Probably

1964.

OF "NO-MECHANISM"

INDUCTION

Richard Frick Chemical

pp. 3239-3243,

of asymat center direction.

activity was

, hut atte-npts to

No.Q*

32’to

determiTe optical

the

directio.1

and lack

rotation?

reactant

of

of wlectivity of

kno?iledge

wre

th:;arted

h-r low

conlicuratior?

absolute

of

thi

and proouct.

In order rotation ether

171i degree

to attack

thiq

and known absolute of a cyclic

Xordin.

allylic

The result?

alcohol,

evidence

Cyclopenten-

with

of the

a clear for

meawra’:lc

we ~113s~ to \&nrk Witll Ihe vinvl type

studied

derronitr;ltion

a cyclic

I>v iii;r;it,~hler

of ,+~~ww’ri

transition

: I : was converted

-01

co~lpar~nds of c’apilv

confieurdtion,

provide

and stereocherri:al

prohlen

to the

and

’ in!! lcticn

Stat?. acid

snd part ialls

sucrinate

a

resolved after

eight

(c=

I, 1 nl!llnaphthyl‘-ethylamine.

with

crystallizations

5 in CHCl,)

with

[ali

ether

of the

and gave,

-:.

b.p.

vinyl&ion

procedure of

from

aluminum

reqcneratcd

acetnnitrile hydride

The alcohol

had

[a:D’

rtduction,

’

,I’

alcohol

~‘a5 converted

to the vinyl

0

il?

mm.:,

[a];’

of Watanabe

Rearrangement

salt

on lithium

+)7.~{@ /CL 5 in Ccl,‘.

(II),

The ,uccinate

i &‘I II at

‘ 1’

and Conlon l!‘O-l’;‘O

‘r-.

, by the

. in Ccl,

trans-

.

in a sealed

tube

under

nitrogen

c yielded -14.0’

(-;

cyclopente;7e-;-acetaldehyde

(c= ii in Ccl,),

by characteristic (triplet)

at

bands

:1--a

The aldehyde

in 51 $ yield.

infrared 0.33

(111 I, b.p.

at

3.“”

7, and was converted

and

‘lj

IJml\,

[3$’

iunct ion was ldentif

c.-/

p and the

to a yellow

n.rr.r.

ied

signal

,!,-dinitrophenylhydra-

0 zone,

m.p.

H, 5.36).

101-10;

iFound:

hidation

of III

with

alkaline

(IV:,

b.p.

?‘,-“i

pentene-j-acetic CHCl,), the

acid

identified

derived

C, $.l;

by comparison

iodolactone

with

those

of

H, .Q. I(.

C1:H1,N,O,

silver

oxide

rewires afforded

(O.‘)r mm\ , [cl]”c

infrared of authentic

spectra

-1

of both

samples.

C,

.‘;

(-1

cvclo-

,g

cc:

II in

the

acid

and

3241

No.44

Absolute pentane

Configurations.

carboxylic

Chart

I;

(-1

acid

V uas

:V‘

of

the course of

their

work

conversion

the

demonstrates is

-cis

to

sistent

with

proved at

~

R-i+:

that the

the

the

It serves chorismic

may also

II

ether

cyclic

II

being

to

in

t!>at

at

/ I_

of

one

~inont.

:_

and Sternaerg acid.

aldehyde in the

II;

1

ip

The

*bus

rearranganent

a exclusion

cert.ainly

nc.er,

now,

until

asymwtric

steric

in

--neth\~lcycloperlt

chuulirooeric

fox-me_

but

.-ketoc,zclo-

outlined

by Mislo;,a

broken,

n definable

enter

direction,

to

con-

speciLical!v a C-C bond

provide?

a

configurations. the

rearrangement

stcrecchemical

to

K_:

bond

(4,

to

reactions

t-he R-L

mechanism

a C-O hond

correlating

iV1

of

configuration

bond

of

be noted

related

to

new carbon-carbon

center,

as an excellent acid

on the

accepted

of

senuence

converted

vinyl

The conversion

method

been

IV was established

carbon-oxygen

a new asymmetric

valuable

i-1

I has

by the

subsewently

The R configuration

of

(-1

prcphenic

model acid

for

(VII 1.

of the

11 to

III

enzymatic

Al,:hough

this

repnrted conversion renction

here of was

.,oca; CH,

T

b

dH 2-h

OOH

VI

so t

COOH

VII

N0,‘t.i

3243

REFERENCES

1.

2,

I.

This

(365 (19Qr .

iKG_6563) .

R.K. Hill and M. Rabinovitz,

Paper I of this series:

Alfred

investigation

from the Public Health

P. Sloan Research

in "Molecular

Interscience

Publishers,

to who% we express

Rearrangements',

i-.1

!I.

E.R. Alexander

,.

A.Gj. Burgstahlrr

New York, N.Y.,

IQ:?, p. 6::.

and I.C. Nordin,

i.. K. Alder and F.H. Flock, Jr., Ph.D.

Ber., 2,

7.

H.A. Vaughn,

2.

We wish to thank the General

Cl. W.H. Watanabe

ed.,

For a recent

and G.F. Bailey.

J.

(1:%-j).

and R.W. Kluiber,

of this resolving

grant

our thanks.

Part 1, P. de Mayo,

study, see J.W. Rails, R.E. Lundin,

Org. Chem., x,

10.

Service,

by a research

Fellow.

s.J. Rhoads,

mechanistic

was supported

J. iti. Chem. Sot.

J. Am. Chem. ibid., Q,

Sot., 2,

:4'O!t(I'<1 .

1;' (lUr,l).

1732 (I?-',.

Thesis, Columbia Aniline

University,

l?"a.

and Film Co. for a generous

Fift

agent.

and L.E. Conlon,

Y. sate. S. Xishioka, Bull. (Tokyo), 11, 570

J. Am. Chem. Sot., 2,

0. Yonemitsu,

and Y. Ban, Chem.

+.?i (1',57'. and Pham.

(lqb?!.

11.

K. Mislow

and I.V. Steinberg,

I-.

F. Gibson

and L.M. Jackman,

J. Am. Chem.

Nature, 3,

SOC., r,

;i';

i1,6‘!.

3307 (19:s).