Spirovetivanes from silylated 1-hydroxycyclopropanecarboxaldehyde.

Tetrahedron Printed in

Letters,Vol.25,No.l2,pp Great Britain

SPIROVETIVANES

FROM SILYLATED J.P.

Laboratoire Universite

SUMMARY

: The

nols.

de

Barnier

In

the

and

have

desilylation

of

preceding

and

enol

been

cyclopropanol

which

derivatives, been

Salaiin”

reported

spirovetivane,

prepared is

from

intermediates

silylated

convenient 1 _,

ether

undergo

key

of

the

l-vinylcyclopropa-

featured.

a

communication tetrahydropyranyl

has

a

ethers

cyclopropanecarboxaldehyde

annulations

J.

des Carbocycles, ERA 316, Bdtiment 420 Paris-Sud, 91405 ORSAY CEDEX, France

sesquiterpenes,

A selective

l-HYDROXYCYCLOPROPANECARBOXALDEHYDE.

ecan-2-one

spiro[4.5]d

CL.53 spirobicyclic

0040-4039/84 $3.00 + .OO 01984 Pergamon Press Ltd.

1273-1276,1984

synthesis efficient

either

readily

of

the

l-hydroxy-

precursor

specific

(1).

of

four

or

l-vinylfive

ring

\ bo ySiMe3

OR

OTHP PC

CHO -1

2a

R = THP

; _

= H

_C This membered

ring

phosphorane butoxide

in

of

the

by

(3)

give

to

(5),

which

framework

has As

propane

systems

been

the

a

matter

-4

(7)

corresponding

TLC,

650°C

enol

found

in

target

of

and

of -5

fact, (8)

silyl

the has

a

partner

aldehyde

78% yield. (PPTS)

the

(2)

Removal in

of

syntheses thermal

1273

of

ethanol

10 ms -2c underwent ether of the Spiro [4.5]

been

choice

for

five-

the

at

t-

THP group

55”C,

within

which can be -2b, 2c, in 95% yield C3 & C5 spiroannu-

1-vinylcyclopropane

for

vanes.

of

_1 with cyclohexylideneiodide and potassium

l-vinylcyclopropanol

sesquiterpenes many

of

in

1-trimethylsiloxy

at

also

phosphonium 2a

provided

the

thermolysis -2a. On flash lation into the regiospecific carbone

be

p-toluenesulfonate

from

basic

to

reaction

vinylcyclopropane

pyridinium

monitored

silylated

the

-3

SiMeg

=

appears

So, Wittig

from

THF gave

means as

synthon

Spiro-annulation. prepared

of -2a by 3 hours then

attractive

0

-

the

d ecan-2-one

spirovetivane

or

-3 acorane

(41, class

(6). ring

recently

enlargement used

to

of

prepare

the some

vinylcyclospiroveti-

a

1275

Addition ry

gement

into

the

expansion,

of

one

equivalent

in the -10 which, 2-vinylcyclobutanone

cyclohexanol

see

ref.

of

same

methyllithium

conditions (For

-11.

to

(EtOH,

the

enone

PPTS,

examples

-8 gave

of such a ready

O-Si-

%

tertia-

rearran-

C3+C4

1). OR

the

underwent

40’)

ring

x

0-Si

-

\ P(

ti

To

achieve

the

1-(t-butyldimethylsiloxy) available

of

imidazole

DIBAH by

(16)

of

the

aldehyde

at

by

the

GC.

is

(t)

and

1655

cm

such

as

in

ppm -1

-15,

energy

(15).

amount

of

in

Application _1 led

M of

then

to

in

DMF in

the

the

reduction

resulting (17)

Piers

provided

-14 in

the

the readi-

of

2 equiv.

of

-12b

with

cyclopropylcarbinol

procedure

enone

prepared of

presence

Then,

the

siloxy

_6 we have treatment

Thus,

-12b. of

of the

of

two

the

other derivative highly

cyclohexanones triethylamine ClSiMe

3

(1 ~1)

the

the

(8)

aldehyde

which

allowed

73% overall

of

a

shown,

desilylation

(19)

methanolic

:

at

yield

from

enone

solution

of

of the

(containing

48 lJ

(25

d

in

IR

the

22%

(5)

at

1645 bond

activation

of

upon

and

4.25

vinylic

an

; while ~1)

a

shown

six-membered

required

obtained hr

gave as

at

-14 produced 1750 cm-l ).

was for

and

frequencies

of

correspon-

78/22,

protons

lowering

17

the

compound of

conjugation

cm-l7

30°C

this

five-

by

of

1710

into

ratio

of

stretching

thermolysis

0

of a

vinylic

-17 ( J C= 0 : 1710 and

-19 ( 4 C = in methanol to

: two

bond

, Ether)

”

600°C 18 in ether

rearrangement

flash

selective

data

previously

thermal

hand,

at

-17 and enol silyl

double

As the

ClSiMe,

ethers

spectroscopic

NMR and

(LDA,

thermolysis

enol

the

facilitates On

converted

Flash

, respectively.

desilylated

epimeric

addition

molecule -13.

dimethylsulfoxide

presence

with

Then,

0.1

-12a. 8 from -

-14 was ether -15. disilylated

The

consistent

4.55

with

target

oxidation

activated

enone

Spiro

capillary

and

the

by

from

enone

trimethyl

of

ketones

the

-13.

enol

mixture

followed

chloride

yield of

The ding

-7O”C,

oxalyl

-13 in 94% overall the preparation

of

C1SiMe2t.Bu -12a (1) with the silylated cyclopropanol

gave

toluene

means

synthesis

0

-14

cyclopropanecarboxaldehyde

hydroxyester

in

9j

-13

-12a R = H b = SitBu(CH3j2 _

ly

CHO

COOCH3

for

important

into -18) treatment instance,

after

2

mn

1276

at

lO”C,

1710

quenching

and

with

NEt3,

of

the

so

formed

HCl,

gave

the

dione

(9C=O

20.

:

1750 cm -l) .

%

O-Si-

x

O-Si-

\ \

‘$$

HOG -20

-19 addition

Finally,

of

IMgCH3

to -19 desilylation

underwent dehydration and -21 which acid in refluxing benzene to provide the

major

compound

NMR spectra ful

to

5,

isolated

identical

Professor

with

G.

Buchi

of

for

J.

Ollivier

and

2)

N.

Miyashita,

3)

R.G. Visser, 70 (1980).

J. A.

Salaiin,

and

Bos

and

5)

J .A. Marshall, 283 (1974). 3: 2’

S.F.

6)

K.P. Subrahamanian and W. Reusch, and Y. K. Hayashi, H. Minakata cites therein.

7)

Tu-Hsin

8)

E. Piers and C.K. Lau, Synth. and I. Nagakura, Can. J. Chem.,

9)

See

10)

D. Caine, A.A. Org. Chem., -41,

11)

ref.

G.

5 in

Buchi,

-41, 3208 12) 13)

and

N.H.

Paquette,

B.M.

15)

J.

and and

16)

E.J.

Corey

17)

A.J.

Mancuso,

and

18)

G. X.

R.

P.H. J.

in

J.

Org.

Rec.

MeOH)

which

gel,

exhibited

IR and

(We

are

grate-

very

Tetrahedron Commun., -61, 288

communication.

Chem.,

Trav.

-42,

Chim.

methanolysis

of

-Fortschr.

Tetrahedron Inubushi,

S.T.

Chao,

Decorzant,

A.

Scudder,

Ollivier,

J.

Nouv.

A.

Huang

France

20

and

Y. of

Org. J.

Venkateswarlu,

S.L.

Stork and P.F. Hudrlik, Creary and A. J. Rollin,

(Received

from

3772

(1977).

Pays _3 gave

Chem.

Bas, the

Org.

-99, Spiro

Naturst.,

Lett., 3789 (1978) ; T. Ibuka, ibid, 159 (1979) and references

Lett.,

-23,

7, 495 (1983).

3227

(1977)

(1982).

; E.

Piers,

C.K.

Lau

Ingwalson,

J-

11. Boucugnani, 1539 (1976).

D. Berthet, (1976).

Trost

Salaiin

alcohols

p -toluenesulfonic

-6).

Anderson,

H. Minakata, T . Ibuka, K. Hayashi, -57, 1579 (1979). Trimethylsiloxy group as substituent vinylcyclopropane-cyclopentene thermal (see ref. 14 and 15).

14)

19)

and

(8,lO).

accompanying

Grieco,

C1SiMe3

Brady

L.A.

ref.

of

epimeric

spiroenones,

on silica

enone

Lett.,

in

(a

of

enone

Brandsma,

Acidic induced [4.5]decan-2-one.

the with

AND NOTES

P.A. L.

4)

Yan

drop

of

Tetrahedron

Yoshikoshi

H.J.T.

gave

treatment

a mixture

this

spectra

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