Novel oxidative rearrangement of β,γ-unsaturated ketone hydrazones on iodination in base

Tetrahedron PrInted In

Letters,Vol.23,No.39,pp Great Britain

0040-4039/82/393991-04$03.00/O 01982 Pergamon Press

3991-3994,1982

NOVFL OXIDATIVEREARRANQ-

Ltd.

OF ~.Y-DNSATURA~

XJiTONE RYDRAZONESON IODINATIONIN BASE Michael Department

Iodlnation

Abstract: the

expected

vinyl

A general the

of

3

base.

which

produces

was

the

can

of

4.

2.

This

5.

chromatography

optically

1. 5.6

ethanol

in

followed

in

the

nucleophzlzc for

also

of

the

via

2 was prepared

The hydrazone

3 was

prepared

compound

of were

(289c yield

by distillation.

obtained from Its

3)

at

could

to

be was

treated

additron

separated

from

determlned

to

from

to the

gem-

with enone

investigate

optically

racemza

of

the

the

transformation

zn diethyl

in

of

treatment

iodide

a mixture

excess

rearrangement

and chose

of

of

of

a bicyclio

oxy-Cope

treatment

25’C.

in 35% yield

structure

3991

by

presence

upon

7 steps

treatment

amounts

of

to vinyl in

the

iodide

synthon

3 was

triethylamine

in addition

the

varying

hydrazone

hydrazone

hydrazone

in

an anionic

enone

12 equivalents

ether obtains

AD-ring the

90024

gave,

involves

vinyl

active

When the

ketones

desired

steroids

Californza

trzethylamine

diethyl

often

rearrangement

necessary

989c yzeld.

The new compound

into

active

active

The ketone

ketone

and

s novel

from

iodine one

converted

Angeles,

5.

iodzdes

iodide,

optically

an optically

4 and a new nonpolar

azlne

report

of

Iodide

iodine

vinyl be

product.

in

equivalents

frequently

an aromatic

enone

hydrochloride

the

Los

product

vinyl of

Batfreld’

2 zn excess

aromatic

of

L.

Calrfornia,

hydrazone

2 equivalents

to

synthesis

enone

preparation

with

and Gregory of

rearranged

to

Wzeland-bflescher

the

the

ketone

we required

indenyl

iodide

for

the

We now wish

s planned

specific then

A.

which

strong

sequence,

iodrde

‘1

University

bzcyclic

In addrtzon

dirodzde

4

the

the

trfethylamzne.3

For

Chemistry,

of

method

hydrazone

ins1

of

E. Jung

the

2 nlth ether

hydrazzne with

desired

startzng iodide

active

vinyl

material 4 by

two

silica

to be 4.7-dxmethylindane

and gel 2 by

3992

Me

Me

exammatron 5

111

of

the

Me

4

5

(7%)

(28%)

spectral

data

shown in Table

-6

1.

The infrared

spectrum

matches

that

MS: 1460l+)

lH NMR:

1.

6.85,

lH,

s

2.82,

2H.

t,

2.21,

3H. s

2.18,

lH,

Suectral

Data

for

13c NMR

IR:

142.6(d)

J=7Hz

quintet,

5

3019(w)

130.9(s)

2900(s)

127.0(s)

2830(x)

J=7Hz

31.7(t)

1495 (la)

24.2(t)

1440(m) 805(m) cm-l

18.9(q)

The mechanism zones,

which

account

for

the

formatlon

of

the

formation

of

(path

the

& on carbon Proton

of

directly a).

Removal

type

of

Thus,

N-lodohydrazone

produces

(path

vinyl

iodldes

an Intermediate

removal

Wagner-Meerweln

Ion -12 either 11

formation

of 4 and 2 (Scheme).

ion lo.

Bowever,

cation

for

as an Intermediate

Iodlnatlon

4.

oarbonium blnyl

the

lodocarbonzum

Iodide

proposed

involves

produce

pound 8. the

for

11teratnre.’

Table

should

reported

b)

the

from u

iododiazonlum treatment 1 which

by

a proton

double

of u

could

of 2 ulth

lodxne

salt

trlethylamlne can

give 2,

would also

trlethylamlne

the

be modlfled

to

and triethylamlne

loses

then

occur

from hydra-

allphatlc

which

bond partiolpation

from 12 with

dllodldes3

salt,

would

rododiazonium

rearrangement or with

and geminal

dlazo

nitrogen

produce

comto

the vinyl

to give

the

via

cyClOPrOPyl~~r-

would

the

afford

tertiary

the

give

Me

Me

Scheme cyclohexadrenyl give

the

iodide

observed

intermediacy

of

product the

enone 2 is

the

expected

mediate

such

trichloromethyl

2.

of

treated

vinyl

whrch would

chloride

as 15a anion

is

(42%), formed

generate

of

to

the

ions

such

which

can lose

chlorocarbonlcm

Me 0

Me

of

to

In carbon of

base-catalyzed

rearranged

as u

a 21% yield

the

undergo

rn the mechanism

trlphenylphosphrne 14

or m to

ion u

halocarbonrnm

with

be expected

The production

lodocarbonlum

The rearrangement the

l3,

product

is

lodlnatlon

indanes

is

of

hydrazones

5.

triphenylphosphsne

lose

HI to for

process.

Thus,

-15a X = Cl -15b X = Ccl3

-H+

-HCl -16

Me

when

in addition

to

an Inter-

chloride

ion

a proton

to

g$+ol> Me

the

in base .3

Presamably,

and either can then

of

evidence

one obtains,

4.7-dlmethyllndane

This

further

a general

tetrachlortde’

ion 16.

elimination

Me -14

-5

(42%)

(21%)

or give

3994

u

or undergo

chloro-

the

rearrangement

and bromocarbonium

ions

such

We thank

~&&~g~. National

described

Institutes

of

Health

to

as 16 have

the for

above

Air

Force

partial

been

support

Camille

and Henry

Dreyfus

5.

of

of

in

other

Scientific

this

rearrangements

systems.

Research

of

9

(Grant

81-0185)

and

research.

and Notes

1978-83;

Teacher-Scholar,

Wagner-Meerwein

described

Office

References 1.

give

Fellow

of

the

Alfred

P.

Sloan

Foundation,

1979-81.

2.

Fellow

3.

a) D. H. R. Barton, and

of

S.

the

Chevron

Sternhell,

S. Sternhell.

Oil

Co.,

Inc.,

R. E. O’Brien, Aust.

ibid..

J.

Gntzwiller,

P.

6. The conversion

and

UCLA.

S.

Sternhell,

J.

989 (1970); c) J.

Chem,, 2,

Chem.

Soctr

470

R. Campbell,

(1960);

b)

A. Pross.

and

A. Pross

24, 1425 (1971).

4. M. E. Jung and J. P. Hudspeth,

5. I.

at

Buchschacher.

of 1 into

2 in

J. Am. Chem. Sot.. a,

and A. Forst.

7 steps

and

Svnthesis.

14% overall

4309

(1978).

167

yield

(1977).

will

be described

in

Tetrahedron,

18.

detail

elsewhere.

7. a) R. D. H. Murray. b)

J.

Rntel,

8. N. S. Isaaos

9. A. Pross

(Received

Analvt.

W. Parker,

and D. B. Jhaveri.

Chem,, 25, 612 (1954).

and D. Kirkpatrick,

and S. Sternhell,

in USA

R. A. Raphael,

21 June

J.

Chem.

Sot.

Chem.

Commun.,

Anst. J. Chem,. 24_, 1437 (1971).

1982)

443

(1972).

55 (1962);

the