Synthesis of methyl ketones by rhodium and ruthenium catalyzed oxidation reactions under phase transfer conditions

Tetrahedron Letters,Vo1.24,No.47,pp Printed in Great Britain

SYNTHESIS CATALYZED

Abstract:

OF METHYL

KETONES

OXIDATION

REACTIONS

Krzysztof

Januszkiewicz

Institute

for Research

Ottawa-Carleton Department

5163-5164,1983

of Chemistry,

University

In the preceding

one to effect oxidation

ammonium

salt critical

ruthenium

and rhodium

Exposure catalyst,

compounds

of 1-decene

and Graduate

Studies

Ottawa,

in Chemistry,

Ontario,

Canada

KlN 9B4

chloride,

also be achieved compound3.

Several

and [Ru(CO)~C~~I~

hydrated

interesting

when compared

Crhe procedure

to take place.

inactive

for the palladium or ruthenium

products

chloride,

differences

reactions

catalyzed

catalysts

reactions.

only diketones.

of dienes However,

of diketones,

using rhodium

complexes,

a Wacker-type

reaction

the rhodium chloride

Second

isomerization

and isomerized

reported

since water

inhibits

the reaction,

catalyzed

oxidation

in contrast,

5163

oxidation

chloride,

ammonium

ions,

Wacker

(THS), which

is

catalyst

for

occurs with THS (it as the catalyst-

Third,

the palla-

is selective,

is not selective,

of olefins

appears

to ketones

as the catalyst.

and co-catalysts

(i.e., copper does not participate reaction,

the reaction

oxida-

First, the

dienes.

the homogeneous

rhodium(II1)

transfer

usually

or 1,9-decadiene

in the case of rhodium,

catalyzed

catalyzed

sulfate

not formed with palladium.

hydrated

are not necessary

hydrogen

with CTAB, using rhodium(I)

including

chloride

and ruthenium

as the catalyst.

permit the palladium

such as 1,7-octadiene

monoketones,

In 1978, Mimoun and co-workers4

could

a rhodium(I)

dichlorotris(triphenyl-

is of some use as a phase transfer

were, with one exception,

reaction

[(1,5 HDRhCl)*l,

reaction.

tetrabutylammonium

it) and to a lesser extent,

to that

while tris(acetylacetonato)ruthenium(III)

between

reaction

(CTAB) as the

was identical

occur using small or large quaternary

phase transfer

catalyzed

as the metal

bromide

This transformation

could also be used, including

for the oxidation

Specifically,

also takes place without

chloride

the use of

to ketones.

chloride

in metal catalysts.)*

with the use of palladium

catalyzed

reaction

catalyzed

compounds

rhodium

(Wacker-

catalysis

describes

of olefins

and cetyltrimethylammonium

in 44% yield.

and ruthenium(II1)

while only large lipophilic

giving mixtures

benzene,

for the change

were ineffective

and ruthenium

isomerization

2-decanone

except

ruthenium

There are several

the rhodium

for the oxidation

to ketones

of the quaternary

This communication

with the dimer of 1,5_hexadienerhodium

phosphine)ruthenium(II)

tion reactions,

water,

of olefins

that phase transfer

with the structure

of the reaction.

as catalysts

to oxygen,

oxidation

we reported

under mild conditions,

as the re-oxidant,

agent afforded

using palladium

affording

CONDITIONS

and Howard Alper*

catalyzed

communication*,

to the success

cupric chloride

phase transfer

dium(I1)

UNDER PHASE TRANSFER

of Ottawa,

Much work has been done on the palladium

rhodium

BY RHODIUM AND RUTHENIUM

The use of rhodium and ruthenium complexes as catalysts for the phase transfer catalyzed oxidation of olefins is described, and compared uiththepalladium catalyzed Wacker reaction.

type reaction).' enables

0040-4039/83 $3.00 + .oo 01983 Pergamon Press Ltd.

such as cupric

in the oxidation). to be a genuine

This is not

Wacker

The phase process

5164

since it is not inhibited TABLE

by water,

and a co-catalyst

[CuC12.H20],

is required.

1 OXIDATION

OF OLEFINS

Substrate

RHODIUM AND RUTHENIUM

Metal Catalyst

PHASE TRANSFER

R4N+X-

CATALYZED

Products,

% Yield

1-Decene

RhC13'3H20

CTAB

2-Decanone,

[1,5-HDRhC112

CTAB

2-Decanone,

34

[1,5-HDRhC112

THS

2-Decanone,

40.

Rh2(OAc)4

THS

P-Decanone,

21

RuC12(PPh3)3

CTAB

2-Decanone,

64

RuC12(PPh3)3

THS

2-Decanone,

28

RuC13

CTAB

2-Decanone,

13.

RhC13'3H20

CTAB

P-Dodecanone,

35

[1,5-HDRhC1]2

THS

2-Dodecanone,

25.

1,7-Octadiene

[1,5-HDRhC1]2

THS

2,7-Octanedione, 5. Diene isomers, 67

Octenones,

1,9-Decadiene

RhC13'3H20

CTAB

2,9-Decanedione,

8.

9-Decen-2-one,

[1,5-HDRhC112

CTAB

2,9-Decanedione,

9.

Decenones,

6.

Deceneones,

Internal

[1,5-HDRhC112

1-Dodecene

44

decenes,

Diene isomers,

Diene isomers,

a2:l ratio of 7-octene-2-one:

internal

octenones.

b

decenes,

44.

35

2-Decene,

Internal

5.

dodecenes,

56.

27a 33

28

43

2,9-Decanedione.

THS

[1,5-HDRhC112

Internal

23b

67

3:l ratio of 9-decene-2-one:

internal

decenones.

ACKNOWLEDGEMENTS We are grateful Council,

for support

to British

Petroleum,

and to the Natural

Sciences

and Engineering

Research

of this research.

REFERENCES 1.

J. Tsuji,

2.

K. Januszkiewicz

3.

B. Heil, S. Toros,

4.

H. Mimoun,

(Received

Pure Applied

Chem., 53, 2371 (1981).

and H. Alper, Tetrahedron S. Vastag and L. Marko,

M.M.P. Machirant

in

Lett., preceding J. Organometal.

communication. Chem., 2,

C47 (1975).

and I. Serge de Roth, J. Amer. Chem. SOC., 100,

USA 9 August

1983)

5437 (1978).