Organic syntheses with sulfones (Part XXVIII) ; synthesis of terpenoid compounds by way of Michael addition reactions to conjugated dienyl sulfones.

Tetrahedron Letters,Vol.24,No.l7,pp Printed in Great Britain

ORGANIC SYNTHESIS

1783-1786,1953

SYNlHESES

WITH

SULFONES

(PART

COMPOUNDS BY WAY OF MICHAEL

OF TERPENOID

0040-4039/83/171783-04$03.00/O 01983 Pergamon Press Ltd.

XXVII

ADDITION

B )

;

REACTIONS

TO CONJUGATFD

DIENYL

SULFONES. M.

:

Abstract yielded by either

dienyl

obtained

Addition

-1.

by

1’Ecole Paris

and ketones transformed thermolysis.

lead

CR-B.)

on

of

to

the

Uguen.

allyl-dienyl isoprenoid

readily

sulfones compounds

available z 2 methyl-l,3 1 . A recent paper2descri-

sutfones

a diaCly1

D.

Superieure France.

to into

diallyl

such

and

Normale Cedex 05,

alkylation

reactions

reaction

Ramirez-Muzoz

sulfone

prompted

us

The

3e .4 --

The 4b to

of

addition suLfone

&,

unit

;

the the

and

reaction

R.B.

Various

proved _2

results original

RAMBERG-BACKLUND

nucleophiles

possible

such

leading

as

to

-3a

submit

the

ethanol, CE+Z),

t-butyk -3b

(E)

acetoacetate

3,

s

(El,

ard

phenylthioacetcxe

eventually

transformed

-5.

was are

then

carried

shown

synthon

in

out

the

table.

a

through

under It

double

Meyers proved

conditions indeed

4a

possible

or to

by

a two

step

attach

an

Yield

CX)

bond.

REACTION zF

“J+%T&

RUz

Substrate Product ---------------_----------__-__--_--____--_____-_____--_--____________________________________ 6a, R=H & , R=H

a2

2,

R=Prenyl

&,

R-Prenyl

55

2,

fi=Prenyl

‘,

R-Prenyl

91

4_ ,

R=Prenyl

-75a

R=Prenyl

50

5 _I

R=PrenyL

_a5b

R=Prenyl

70

10

to

letter.

the

dure

of ethanol which were reaction or

are

M.

Mulhauser,

additions

Ramberg-Backlund

present

M.

de Chimie de Lhomond, 75231

sulfones

sulfinate

the

into

Lave,

Laboratoire 24 rue

Michael

butadienyl

to

D.

sulfones di-allylic Ramberg-Backlund

A(kyl

bing

Julia*,

11

CX= OEt)

1783

ai

proce-

isoprene

The

possibility

polyisoprenoid -9

-10 -

the ving

compounds

-

-11

corresponding the

uay

primary

chloride

to a recurrent

way

isomeric

corresponding

and

of

a recurrent

investigated

carried

out

11

:

method starting

as above.

CX=CL)

for

the

with

benzyl

Conversion

followed

by

building-up chloride

of the

another

of unsaturated

ether

alkylation

the -11

steps

CX=OEt)

gave

-12 thus

into pa-

isoprenylation.

joining

tertiary

the 6

Stewart

allylic

out

then

were

by Lacombe

The the

was

CX=OEt)

A different pioneered

of working

units

to the

growing

chain

was

readily

available

by

under

palladium(O)

the

pyrolysis

.

allylic

esters

isoprene

sulfones

with

the

-13 are

now

dienesulfinate

1

treatment catalysis

of

7.

PYROLYSIS

Substrates

Mixture

composition

&,

-15c

5a

(60),

-15a

(58), -16a

(26),

-15a

(651,

(35)

R = Prenyl

E,R=H

J/g, *

R = Prenyl

unidentified

isomeric

Addition

of

either

CR = H, Prenyl)

which

head

to tail

coupling

Clavandulyl

ACKNOWLEDGMENTS

:

&

Total

(191,

(14)

Yield

(X1

(21)*

*

60

products.

14ac

products

16a -

(XI

ethanol were

or

t-butylacetoacetate

pyrolysed

accompanied

by

minor

at

180-200,C

amounts

of

led to the di-allylic (Table) isomeric

to give compounds

sulfones

predominantly formed

by

the 1-2'

skeleton).

We

thank

the

C.N.R.S.

CL-A.

32)

for

financial

and material

assistance.

1785

RUZ

6 ace 3a;

z

=-Oh

sb;

z ,-cH(CO,t.6”t)-CO-CH, 3~; z =- CH,CO-CH, id ; z =- CHSPh-CO.CH, Se ; z =_ CH,-CMeOH-CH=CHx

7 RdL02J_Jo

\

14abc -

\

16ac -

/%

1786

REFERENCES

1 a

P. Chabardes,

M.

Julia,

A. Menet,

Ger.

Offen.

b

P. Chabardes,

M.

Julia,

A.

Ger.

Offen.

c

D. Cave, Waard

These

and

H-0.

Huisman;

2

F. Naf,

3a

The

stereochemistry

ven

a satisfactory

4a

Decorzat

will

be

C.Y.

Meyers,

Buchi

5a

R.

described

and

Catalytic

Menet,

Ingenieur-Docteur,

A.M.

R.M.

Paris

VI,

2319518,

Chem.

Abstr.

so,

27403

(1974)

2319983,

them.

Abstr.

80,

26750

(1974)

1978

Tetrahedron,

37,

and

S.D.

Escher,

Tetrahedron

will

be

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Matte

the

W.S. J.

gave

Letters,

full

Chem.

C'H,

details

Mathews,

1-B-R-A.

J.

b

Chen,

E.R.

De

have

gi-

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Chem.

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5043.

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in the

Am.

SOC.,

1982,

paper.

spectrochemical

Am.

Burger,

(1980).

in the

experimental

and

Freidinger,

hydrogenation

and

417

; J-J.

compounds

1-R ., Mass)

data

which

paper.

91,

7510

(1969).

b

G.M.

(1974).

hexahydrofarnesylacetone.

b

Catalytic

hydrogenation

dihydroisophytol.

6

E.M.

M.

Lacombe

Julia,

M. Nel,to

a

Part

XXVII

and

8.

M.

Nel

and

be

published.

, J.N.

Stewart,

C.

J.

Am.

Saussine,J. Some

Verpeaux

other

and

M.

Chem.

Sot.,

organomet. examples

Julia,

(Received in France 4 January 1983)

83,

3457

them.,

will

be

Tetrahedron

x,

(1961).

181

described

Letters,

(1979) in the

1982,

; M. Julia full

4319.

paper.

and

gave