Synthesis and pyrolysis of cyclic sulfonium ylides

Tetrahedron Letters,Vol.28,No.4,pp Printed in Great Britain

SYNTHESIS AND PYROLYSIS Huw M.L. Department

Intramolecular

Abstract: -------results

in

the

We have ylides

of

reagents

of

initiated

a

general in of

carbenoid

intermediates

a series

of

to 1,

of

these are

such by

T.

Forest

order

In

this

determine

paper

we

is

by

rearrangement ring

derivatives,

>

extend prepared

that

related

react

isolable unstable capture

sulfur

procedurej.

of

ylides

Examples

of

with

these

stabilized

cyclic

ylides

series

of

sulfur

were followed

approach

to

the

suitable

precursors 371

to by have

carbenes

by

has

developed

been

stable

prepared by

form

electron

also

been and

into

ylides,

alternative In

of

cyclic

16-8

and

examined

are

5

an

stable

the

useful

however,

deprotonation.

synthesis

a

lo-thiaanthracene by

sulfonium

two

sulfides2a’3

cyclic

and

compounds at

sulfides

when

3,4-dihydro-2-thianaphthalene4

carbenoid a

carbenes

Several

alkylation the

“( R

readily

and

involving

observed

(CH2)n-

are

of

to

of

the

(QoEt

Rh2(OAc)4

intramolecular

expansion

limited

capture

0

known

these

groups2.

generated

as

facile

-2

well

withdrawing

sulfonium

size.

-1

and

the

examined

the

ylides.

utility

describe

also

that

ring

sulfides

stable

intramolecular

found

N2 (CH2),SR

It

of their

0

OEt

ylides

by

sulfonium

chemistry

to

by

on

University,

cyclic

. We have have

Crisco

intermediates

the

compounds

YLIDES

NC 27109

stable

examine

dependent

p/c 0

of

in

and

Van

carbenoid

sulfides’

ylides highly

SULFONIUM

Winston-Salem

series

study

L.

Wake

of

synthesis.

synthesis

rearrangements

a

structure

organic

thermolysis

7486,

capture

formation

and

Chemistry,

Box

P.O.

OF CYCLIC

Davies*

of

0040-4039/87 $3.00 + .oo Pergamon Journals Ltd.

371-374,1987

method order

their

to

ylides,

372

rhodium(II)

acetate

In added

a typical

over

acetate

in

was

acetate

to

give of

the the

ring

only sulfur

group

Even undergo

4 will

though

smooth

ausbstrates

be

the to

of

five the

5,

the

and

occur.

this

beta ---

is

ylide analogous

decomposition

the

to of

ylide

the

has

this

over

the of

they

However,

none type

milder

conditions

(8O’C)

formed

from

the

rhodi,Jm(II)

phenyl

sulfide

lg. --

This

product

other

the

possible

a highly

ester

carbonyl,

1.4-rearrangement,

unstable

allene

fragmentation ylides

the to

stable

four-membered

give

8,

is

which

catalyzed

from

a

presllmably

would

result

in

-a

_7 of

to

an

acetate

which

an E/Z

oxide.

-6 a new class

to

contrast,

beta hydrogen --ring is

arises

and this

the

fragmentation

the

Finally,

described12.

that

system.

of

ylide 2a rearranged -1,4-rearrangement”. In

2b and -2c underwent -Presumably, the acidic

the

all

ring

product

the

-5 summary,

been

for

ylide

temperature,

while in -2c intramolecular

and

shows

a Stevens

a concerted

under

involving

formation

In

clearly

from

reaction,

allow

The mechanism

the predominant reaction with acyclic 2 , and a similar reaction involving

decomposed

1 ,4-rearrangement favored

is

ring 2f --

elimination

reaction

16O’C.

ylides

to

four-membered

to

respectively.

to

the

stabilizing

room

larger lb.9

decomposition

derived

an overall ring

4.

ring

form

a clean

result

under

ethyl

insertion

hydrogen3

eight-membered ring

heating

of give

this

in at

six-membered of

seven-membered

Indeed,

containing

role

stable

products

product

6 and 1,

formation

to -lg failed was assigned structure but

to

C-H

Although

sulfide

usual

in

of

the

membered

attempts

only

was

heated 8 h,

from

and seven

respectively.

later,

ml),

a further

but

ml)

suspension

recrystallized

five

resulted the

(20

a stirred (100

for

prepared,

an important

in -2b facilitates the sufficiently flexible

was The

le --Id and -3b and 3c, --resulted in

The

the

alkenes

residue

2a-c are quite --rearrangement on

form

dichloromethane

pump to

heating

yield).

discussed

plays

in

dichloromethane

of

1 ,2-rearrangement2*“. mixture

the

similarily

sulfide -If 2f, the phenyl -isolable product of

in After

(67%

ethyl

formation the

22

cyclopentanones

ylide

the

and

pure

2b and -2c were -by decomposition

rings

mmol)

atmosphere.

evaporated give

decomposition. la (5 mmol) -a Sage syringe

of

(0.05

an argon

solvent ylides,

procedure

8 h by means

rhodium(I1) reflux

catalyzed

cyclic

sulfoni>um

ylides

are

readily

373

Table:

Rhodium(I1) Acetate Catalyzed Decomposition of -1

Entry

Substrate

Product(s) Yield (%ja 0

0 Et

1

-la n=2, R=Ph

67%

-2a 0 2

0

-lb n=l, R=Ph

69% 2b'Ph

3

-IC n=3, R=Ph

@::5%

pEt 3a o-

2c

4

OEt 64% 3b

0

0

fY

-If

OEt

n=O, R=Et

53%

Et 2f 7

iCH2)2SPh ‘( )Et

-le n=6, R=Ph

-3c

6

CHqSPh L 0

-Id n=4, R=Ph

-

5

16%

-lg n-0, R=Ph

-4

a) Isolated yield

71I

(CH2:)$Ph

374

obtained

by

susceptibility

under

study

and

.

acknowledged.

For

and

recent

a)

Org. ---

Heslin,

W.

Act. ---

a)

Hori,

E.;

Hori.,

M.;

sulfides.

attack

a William

Petroleum

by see:

Slawin,

I.;

Suzuki,

is

now

and

Flora

Research

Fund

lo,

J.;

5223

179;

Moyer,

and

cited

Williams,

W.;

D.J.

Yagihara,

Nakaido,

Of

Feldman,

references

Ando,

T.;

Capture

M.P.;

A.M.Z.;

b)

Toyama,

intramolecular

a)

S.;

T.;

Migita,

T.

2.

1721. Res. --

1984, ---

T.;

Lett. ---Shimizu,

17, --

Shimizu,

1983 ----’

Tomoto,

T.;

by

the

synthesis nitrogen, so,

1403.

Kataoka,

Imai,

by

C.J.;

1977, ---

37 --’

H .;

Kataoka,

and

work

?_?a?,

-’27

Chem. ----

M.;

by

electrophilic

course. this

sez.

Res. --

Act. --

Tetrahedron ----------

due

Moody,

Crg.

‘1986 __-_’

1972 ----’

M.

or

Chem. ---

Imai,

E.

J.

J.C.;

Lett.

Chem. ---

Vedejs,

intermediates

and

of

heterocyclic oxygen

H.

b)

S.;

carbenoid

Corporation

of

sulfur,

Rapoport,

Tozune,

in

support

Research

examples

Ando,

of

nucleophilic

Notes

by

Tetrahedron --------------

5.

reported

of

P.L.;

4.

be

Financial

gratefully

therein;

3.

both

is

carbenoids

2.

will

capture to

Acknowledgement: -------------Hewlett Grant

References -------------------1

intramolecular

Their

26 --’

358. H.;

Kataoka,

3733;

A.

Tetrahedron _--------_

H.;

Tomoto,

b) Lett. ---

A.

M.;

Hori, 1982, ----

T.;

Shimizu,

H.;

Ohno,

lc-e ----

were

prepared

according

Kataoka, 25, --

Tetrahedron -----------

Kataoka,

Tomoto,

M.;

2597;

J.

to

the

Kishida, Shimizu,

c)

Hori,

org.

fiht.

M.:

24 --’

3629.

1990,

3.

1981 ____’

Lett. ----

S.

A.; T.;

2468. 6.

1 a, --

Compounds

1. NaSPh

HO(CH2)nCl

7.

Compound with

lb --

2. 3.

was

prepared

chloromethyl

Compound

If --

acetoacetate

and

diazotization

2.

by

reacting

the

phenyl

sulfide azide

with

prepared

by

lg --

were the

with

,

’ ?+

ArS02N3/NEt3

N2

(CH2)nSPh

sulfonyl

with

scheme:

1. _wOEt

I(CH2)nSPh

SOC12/pyridine NaIlacetone

n-dodecylbenzene 8.

>

following

appropriate

dianion

followed

by

of

treating

with

as

the

base.

dianion

thiolate

n-dodecylbenzenesulfonyl

acetoacetate

diazotization

triethylamine

sodium

ethyl

of

ethyl

followed

azide

and

47, --

4808.

by

triethylamine

as

base. 9.

Taber,

D.F.;

Petty,

10.

Trost,

B.M.;

Melvin,

N.Y., 11. 12.

For

E.H. L.S.,

A.

Org. ___ llSulfur

Chem. ---

1982, ----

Ylides”,

Academic

Press,

New

York,

1975. examples

Vedejs, (Received

E.; in

of

1,4-rearrangements

Arnost,

M.J.;

USA 21

November

Hagen. 1986)

of J.P.

sulfur 2.

org.

ylides

see

GE.

292,

Ref. 22,

4c

and

3230.

5.

OEt