Decarbonylation of thiol esters to give sulfides promoted by transition metal complexes

Decarbonylation of thiol esters to give sulfides promoted by transition metal complexes

Tetrahedron Letters,Vo1.28,No.50,pp.6321-6321-6324,1987 0040-4039/87 $3.00 + .OO Printed in Great Britain Pergamon Journals Ltd. DECARBONYLATION OF ...

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Tetrahedron Letters,Vo1.28,No.50,pp.6321-6321-6324,1987 0040-4039/87 $3.00 + .OO Printed in Great Britain Pergamon Journals Ltd.

DECARBONYLATION

OF THIOL

PROMOTED

Kohtaro Research

Osakada,

Takakazu

Laboratory

Technology,

of Resources

Thiol

decarbonylation

esters

Although alkyl

organic

reactions

aldehydes

Pd(0)

has received preparation sulfides

by catalytic of Rh(1)

of transition is well

limited

chlorides

complexes

Utilization,

known,

promoted

by heating

them

although

sulfides.

and aryl alkenyl

Symmetrical

diary1

through

of Pd(0)

compounds

metal acyl or aroyl complexes 1. its application to synthetic

it will

through

or Rh(1)

sulfides

in the presence

Typical

procedures

(33 mg,

0.050 mmol)

dissolved

of acyl chlorides 2 complexs.

to

and

by Rh(1)

>

and S-phenyl

was evacuated

as confirmed

was performed

isolation

by bulb

Other (PPh3)4,

RhC1(PPh3)3

amounts

of Pd(0)

thiol

complexes.

Ar-S-Ar

P~(PCY~)~

(PCy3 = tricyclohexylphosphine)

flask under

of GLC.

After

1.0 mmol) atmosphere.

3 h, diphenyl

Identification

of NMR spectroscopy column

(214 mg, nitrogen

and Ni(PEt3)4 also causes

Ni and Pd complexes are less effective

spectrometry

on Florisil

decarbonylation

such as Pd(PPh3)4, catalysts

of PhCOSPh

6321

The (100%)

PhSPh

and

after

(hexane)

Pd(dpe)2,

than Pd(PCy3)2.

giving

were

of the reaction

and mass

chromatography

sulfide

to bulb distillation.

zero-valent

esters

p-CH3C6H4-)

at 100 “C.

by short

of corresponding

from corresponding

benzenecarbothioate

by means

by means

of the product

decarbonylation

for

of diary1

cat.

in a Schlenk

and heated

a new method

preparation

complexes.

of catalytic

Pd(PCy3)2

(3 ml)

provide

are obtained

are as follows:

in toluene

was obtained

Ni

amounts

of

compounds.

promoted

(Ar = C6H5-,

followed

into sulfides

Here we report

sulfides

by Pd(0)

Ar-$-S-Ar 0

product

Institute 227, Japan

were

less attention of various

esters

system

Tokyo

Yokohama

to decarbonylation

and alkanes

Yamamoto*

found to catalyze decarbonylation of acyl 4 and acyl phosphonates. Similar decarbonylation of thiol esters

3

cyanides

has been

to alkyl

Recently

thiol

decarbonylation

or aryl complexes

and Akio

Midori-ku,

amounts

SULFIDES

COMPLEXES

are converted

promoted

or stoichiometric

TO GIVE

METAL

Yamamoto:

4259 Nagatsuta,

Abstract:

give

ESTERS

BY TRANSITION

6322

Table

Run

Decarbonylation of Thiol Esters Promoted by Transition Metal Complexes

Substratea'

Conditions

Complex

Ph-C-SPh

(mol%)b'

Solvent

Temp.

Time

Pd(PCy3)2

toluene

100 "C

3 h

toluene

100 '=C 3 h

diphenyl methane

140 '=c 9 h

a

(Yield 8) c)

Product

Ph-S-Ph

(100)

(5) Pd(PCy3 )2

[email protected]

0

[email protected]$)CH3

(98)

(5)

P~(PCY~)~ Ph-i-SCH3 0 (20) RhC1(PPh3)3

Ph-S-CH3

DMF

(100)

(100)

(100) RhC1(PPh3)3

CH3wC-SPh 6

(100)

CH3wC-SPh

Pd(PPh3)4

s

(20)

CH3w

-SPh ci b

(43)d'f)

toluene

100 'C

5 h

CH3'+S-Ph

(62)e'f)

DMF

100 'c

3 h

CH3/C\\/S-Ph

(lOO)f)

DMF

100 'C

3 h C2H5+/S-Ph

DMF

100 '=C 3 h

(1oo)g)

(100) RhCl(PPh3) 3

P-S-Ph

(1oo)g'

(100)

!

of substrate

used was

1.0 mm01

for runs

l-3 and 6;

0.2 mm01

4, 5, and 7-9.

b) Mo18

of complex

c) Determined d) Substrate

to substrate.

by GLC. (46%) was recovered.

e) 3-(Phenylthio)propene f) Ratio g) E/Z

CH3+S-Ph

RhC1(PPh3)3

Ph-C-SPhg)

runs

3 h

(100)

bl

a) The amount

lo0 "C

RhC1(PPh3)3

g)

C2H5+C-SPh

toluene

(13%) and diphenyl

sulfide

of E to 2 was not determined.

= 100/o.

The ratio

was determined

by 1H NMR.

(9%) were

also

formed.

for

6323

RhCl(C0) (PPh3)2, as phenyl

but the reaction

benzoate

conditions.

do not undergo

Reaction

temperature

is stoichiometric. decarbonylation

of Ni(PEt3)4

with

Carboxylic

under

equimolar

similar

PhCOSPh

such

at room

gives

trans-Ni(Ph) (SPh) (PEt3)2, which undergoes 5 of PhSPh. As cleavage of the C-O bond between

elimination

esters reaction

facile

reductive

the acyl and alkoxy

groups

in carboxylic esters has been established to be promoted by Ni(0) le complexes, the overall catalytic reaction seems to proceed as shown in the following a Pd(0) aryl

Scheme,

compound

Pd(II)

which

compound

elimination

involves

followed

to give

with

oxidative

addition

by decarbonylation a thiolato

the sulfide

ligand

with

of a thiol

of the aroyl

and the subsequent

regeneration

ester

ligand

of a Pd(0)

to

to give an

reductive species.

Scheme

Although

S-phenyl

decarbonylation

catalyzed

1-(phenylthio)propene diphenyl

sulfide

of substituted cleanly

(CH3 -CH=CH-COSPh)

also undergoes

the highest

of the desired

1-propenylcarbothioate

was

by Pd(0)

complexes,

62% due to the formation

Decarbonylation

and 3-(phenylthio)propene.

acrylic

acids

using

to give a quantitative

an equimolar

yield

yield

of by-products

amount

of aryl alkenyl

such as

of thiol

of RhCl(PPh3)3

esters proceeds

sulfides.

R\ /H

H/c=c\sph RhC1(PPh3)3 (R = CH3-, The results

of these

reactions

1-butenylcarbothioate exclusively

give

configuration.

and

sulfides The high

(E)-S-phenyl

in Table.

stereospecificity

with

carbothioate

retention

of this reaction

decarbonylation

E-Z isomerization.b -The reactions in the present paper

C6H5-)

@)-z-phenyl

2-phenylethenyl

on decarbonylation

fact that RhC1(PPh3)3-promoted proceeds

are shown

C2H5-,

of E agrees

of a,e-unsaturated

with

the

aldehydes

without

of sulfides, precursors acetylenes,

especially

of various

of aryl alkenyl

organic and olefins. 7,S

compounds

provide

new methods

sulfides,

which

for preparation

are valuable

such as aldehydes,

ketones,

synthetic

6324

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