Oxygen atom transfer by an intermediate in the photosensitized oxygenation of diazo compounds

Tetrahedron Letters Xc. 15, IIF 1317 - 1370. @Pergamon Press Ltd. 1979. Printed in Greet Britain.

OXYGEN

ATOM

TRANSFER

IN THE PHOTOSENSITIZED

Wataru

Department

The photosensitized

Summary: presence

of oxygen

intermediate

was

notably

systems

4)

produced likely

function

oxide

which

compounds

in the

An electrophilicity

that the oxygen

oxygen

et al. showed

Murray

oxygenation

can be trapped

atom

catalyzed atom

oxide, 3) the oxidant

of the

transfer

reactions. transfer

or 1)

that

Some

agents,

from ozonolysis

of

an intermediate

of diphenyldiazomethane

was

by aldehydes

and naphthalene

on oxidation

by singlet

reaction, 8) the oxenoid

oxygenation

of transferring

intermediates

stabilized

diazo

sensitized

oxygenation

/

diazo

out.

as oxenoid

as a part of our studies

transfer

photosensitized

\

of Tsukuba

a most to give

and naphthols 7) , respectively.

atom

oxenoid

apparently

N-oxide, 2) selenium

Recently,

is capable

carried

Kohmoto

Japan

in many monooxygenase

in the photosensitized

ozonides6)

300-31,

of various

to claim

and iodosobenzene. 5)

carbonyl

oxygen

fashionable

is involved

pyridlne

alkyne,

and Shigeo

COMPOUNDS

investigated.

mechanism

chemical

Ibaraki

were

OF DIAZO

The University

oxygenations

atom acceptors

It has become oxenoid

Miyazaki

of Chemistry,

Sakura-mura,

BY AN INTERMEDIATE

OXYGENATION

Halime

Ando*,

0040-4Oj9/79/0408-1?17$02.00/0

of d-carbonyl-stabilized oxygen

produced

compounds

+ 2

'0

2

atom

to sulfides.

have different

of non-stabilized

-

from those

ones.

\/-y -

/

-N20

/

&'C=O 1317

)

\ /

'N=N

-N2 \ I C&j

oxygenation

/

c=o

and

from the

or pyridinium

We present

character

,o-o-

/'+N

produced

sulfur

in the photosensitized

\ C=N

intermediate

oxygen

here

that

ylids the

of d-carbonyl-

in the photo-

1310

15

2::.

In a typical

reaction,

solution

containing

dimethyl

sulfoxide

mixture products

were

benzil(86%)

sulfide

sulfoxide Similar

photolyzed

up by removing

the photosensitized diphenyl

oxygenation

were

Table

solvent

and analyzed

I

ether

benzoate, when

in the Presence

of Oxygen

RC(N2)R'

Acceptor

Solvent

0.2 mm01

1.0 mm01

30 ml

PhCOC(N2)Ph

Me2S0

Me3SiCOPh

--

- _----------

PhC(N2)Ph

Ph2S

* The reaction yields

were

was carried

Diazo

30

ccl4

99

36

CHC13

82

29

98

24%

ccl4

98

29

CHC13

72

26

C6H6

81

3

CHC13

78

14

C6H6

Compounds

Me3SiOCOPh

20%

83

C6H6

I.

--------------41

CHC13

C6H6

benzil.

out in carbon

83 78

46

33

79

_

_-___--------81

1

78

6

out under

_ _-

31

77

by GLC based

of

of the

with

in Table

Ph2SO

Me2S02

92

was carried determined

RCOR'

Et20

CsH6

procedure

Atom Acceptors.*

45%

CHC13 Me3SiCOPh

together

of Various

86%

C6H6

Me3SiCOPh C6H6 ________---Me2S0 C6H6

--_-

similar

in the presence

and summarized

o

The mayor

led to the formation

the reaction

Oxygenation

Ph2S

Using

respectively,

and chloroform,

and 1 mmol

The reaction

by GLC.

sulfone(45%).

Photosensitized

Ph2S

lamp.

of benzoylphenyldiazomethane

also obtained

drethyl

tetrachloride,

300 W Halogen

and phenyl(trimethylsilyl)ketone

in benzene

as sensitizer

using

and dimethyl

and the trimethylsilyl

results

of benzoylphenyldiazomethane

30 mg of tetraphenylporphine(TPP) was

was worked

0.2 mmol

oxygen

with

TPP for 30 min.,

on the diazo

compounds.

and the

No. 15

1319

the yields

Interestingly, oxygenation

of diphenyl

of benzoylphenyldiazomethane

find a large

diphenyldiazomethane

and diazofluorenone.

diphenyldiazomethane

is known

transferring produced

oxygen

reaction

sensitized

rates

oxygenation

The photosensitized oxide

which

10)

system

atom

toward were

of

oxygenation

is smoothly

of

capable

The oxenoid

may have different

and sulfoxidewerenot

of either

of oxygen

in those

of

species nature

from benzoylphenyldiazomethane.

the sulfone

phenyl(trimethylsilyl)ketone sulfone,

produced

in the absence

The relative

difference

and diazofluorenone

species

indicated

conditions

in the photosensitized

to phenyl(trimethylsilyl)ketone.

oxenoid

experiments

9)

to form carbonyl

from diphenyldiazomethane

to its analogous Control

atom

sulfoxide

sensitizer

transfer

diphenyl

determined

formed

or the diazo

in the diazoalkane

sulfide,

dimethyl

from the yield

under

the

compound. and the

sulfoxide,

and

of the sulfoxide,

the

and the benzoate. sens/hv/O2

CH2N2

Me3SiCOPh

+

0.2 nun01

+

Me SO p 2

0.2 mm01

+

Me SiOCOPh 3

ether

0.2 mm01

Me2S02

+ tCH20J

22%

11% sens/hr//02

PhCOC(N2)Ph

+

Me3SiCOPh

+

Ph2S -

Me3SiOCOPh

+

Ph2S0

+ PhCOCOPh

ether 0.2 mm01 The relative Table

II.

sulfide

0.2 mm01 rates

obtained

The large

were

observed

0.2 mm01 from competitive

differences

24%

58 experiments

in the reactivities

in the oxygenation

are

97%

summarized

of silylketone

of diphenyldiazomethane,

and diphenyl

diazofluorenone

and diazomethane. Table

II.

Relative

Rates

in Various

of Oxygen

Diazo

Atom

Compounds-Oxygen Relative

Diazo Compounds

Transfer

by Acceptor

System.*

Rate

Me3SiCOPh

Me2S0

PhCOC(N2)Ph

(1)

6.6

4.8

CH2N2

(1)

2.0

0.01

phti

(1)

0.6 0.2

0.01

N2

Ph2S

in

1320

No. 15

* Competitive

experiment

containing atom

0.2 mm01

acceptors

calculated On the other and dimethyl

hand,

These

diazofluorenone,

the relatively

higher

towards

suggest

the oxenoids

that

and diazomethane

possess

each

yields,

reactivity

of two oxygen

reactivities

after

the oxenoid

solution

2.0 mm01

The relative

molar

was observed

data

out in benzene

compound,

and 30 mg of TPP.

from the relative

sulfoxide

methane.

was carried

of diazo

30 min.

were

irradiation.

of diphenyl

sulfide

from benzoylphenyldiazo-

from diphenyldiazomethane,

less electrophilic

character

than

that

from benzoylphenyldiazomethane. The present indicated calbonyl

and earlier

that essentially oxide

structures

intermediate.

sens/hv/02

atom

transfer

from carben-oxygen

atom transfer

The following

//" -C \ c=&o /

p

obtained

all the oxygen

for the oxygen

ON2 I, II PhCCPh

results

scheme

shows

the possible

from

oxenoid

/O

/O t) -c ~C&D \c __ 0 6 / /

c-t -c

-L

-;11_;_

are formed

from benzoylphenyldiazomethane.

-s-

0

+’

fl iDA -C-C/C \

_&=c/_

0 -z-Si-

00

products

complex

&

0 -;-

-cOSi-

+

00

-;11-;-

References 1) G. A. Hamilton

in "Molecular

Mechanisms

p-405,

Academic

Press,

2) T. Tsuchiya,

H. Arai,

and H. Igeta,

Ed.),

New York,

3) T. Tezuka,

H. Suzuki,

4) R. E. Keay

and G. A. Hamilton,

cited

Tetrahedron

and H. Miyazaki,

Activation"

(0. Hayaishi,

Letts.,

Tetrahedron

J. Am. Chem.Soc.,

2213

Letts.,

(1970).

4885

98, 6578

(1978).

(1976);

references

therein.

5) F. Lichtenberger, 70,

of Oxygen 1974.

939

6) D. P. Higley

and R. W. Murray,

7) s. K. Chaudhary, 8) W. Ando,

W. Nastainczyk,

and V. Ullrich,

Biochem.

Biophys.

Res. Comm.

(1976).

R. A. Hoyt,

S. Kohmoto,

9) H. H. Wasserman 10) A. Sekiguchi,

J. Am. Chem.

and K. Nishizawa,

and I. Saito, Y. Kabe,

Sot.,

and R. W. Murray,

3330

J.C.S.Chem.Comm.,

J. Am. Chem.

and W. Ando,

96,

Tetrahedron

Sot.,

894

97, 905

J.C.S.Chem.Comm.,

(1974). Letts.,

4235

(1978).

(1975).

in press.

(1974)