Novel one step synthesis of epoxides from β-hydroxy-selenides and sulfides

Tetrahedron Letters,Vo1.25,No.40,pp Printed in Great Britain

0040-4039/84 $3.00 + .OO 01984 Pergamon Press Lid.

4569-4572,1984

NOVEL ONE STEP SYNTHESIS OF EPOXIDES FROM @HYDROXY-SELENIDES AND SULFIDES

J.L. Laboureur,

and A. Krief*

W. Dumont

Department of Chemistry Facultes Universitaires Notre-Dame de la Paix 61, rue de Bruxelles, B-6000 NAMUR, Belgium

Epoxides 6-hydroxy

We alkyl

prepared in one step from %-hydroxy which involves dichlorocarbene

are stereoselectively sulfides in a process

have

recently

reacted

bearing

shown

under

the

the

the selenyl

compounds ethoxide

on

that

carbon

&hydroxy

same

bearing

selenides

and

selenenyl

B-hydroxy

conditions

group is attached

are inert

the

and

fl-hydroxysulfides possessing

and produce

epoxides

selectively

R3 and R4 = Alkyls

to

20 hrsjand

disubstituted

occurs

with

to their

permits

the configuration

and

of a wide

ones

(Table).

It proceeds

these

with thallium.

R2 IRS RI--_'y_,C---R4

variety

0

derivatives under

and

has

mild conditions

of epoxides

The reaction

such

is highly

and takes place, at least in the cases studied, at the carbon bearing

the carbon

route b

phenylseleno

thio analogues.

the synthesis

and trisubstituted

(stereospecific)

they react smoothly

T10Et/CHC13 C k $-- R4 R3 = H R3

b"

methyl

whose

(scheme Ib).

X = S,Se R = Me,Ph

both

sulfides

rearrange

We found that whereas

fR

R1--?C-

route g

extended

and

group

I

R2

T10Et/CHC13 4

reaction

selenides

sulfenyl

to one or two hydrogens.

Scheme

The

the

to the two first sets of conditions,

in chloroform

successfully

or

two

to 1 silver tetrafluoroborate on alumiketones in the presence of silver tetrafluoroborate, 3 1 or thallium ethoxide * in chloroform (scheme la). Continuing to work in that area na we

residues

selenides

been

(ZOO, 3

as terminals,

c,f+

bi-stereoselective

with complete

inversion

of

the leaving group.

As already mentionned in the case of reaction leading to ketones we recently repor2 ted, the reaction does not take place in THF, benzene, dichloromethane and carbon tetrachloride Thallium methane

but

chloride

occurs and,

are concomitantly

in these in the formed

solvents

case

of

when

few equivalents

B-hydroxy

(scheme II) besides 4569

phenyl

of chloroform

selenides,phenylseleno

the epoxide.

are added. dichloro

4570

Scheme

+a

II

OH

TlOEt +

+ Ccl2 + TIC1 I

+

SePh

t

CHC13

TICI +

To account

for these

results

PhSeCHC$

we assume

that

to the soft selenium group

(sulfur) atom transforming

and at the same

time acts

+

thallium

B-hydroxyselenides (sulfides) but that it dichlorocarbene 495 which is in fact the reactive

ethoxide

first

On

leaving

-

reacts

species.

chloroform

This further

the selenenyl

as a base towards

does not react directly

on

leading

to

links selectively

(sulfenyl) moiety

the neighbouring

to a better

hydroxyl

group

(scheme II). It

was

reaction that

therefore

under

performing

thane

and

catalyst

tempting,

other the

in

the

in order

conditions reaction

known

with

presence

of

The reaction

takes

Epoxides

purification

is

place

often

in the cases studied They

are

more

carbonyl

however

at room

formed

are

The stereochemical

products.

in

outcome

moieties

in the B-hydroxyselenide) besides

the

epoxides

results

reported

or

due

to

and

as

the

the

We found

in dichloromephase

transfer

arising

faster than the one reported

lower

contamination

(Table)

several

but

exogeneous

their by-

is similar and we never observed

between

the

two

from the formal removal

This

yields by

from a rearrangement.

or their dichlorocarbene

(Table).

to perform

formation.

KOH solution

chloride

is much

little

of the two reactions

(resulting

to try

carbene

close to the ones we find using the method A.

differences

striking

olefins

ammonium

temperature

compounds

conditions

hypothesis

and 50% aqueous

comparable

laborious

transfer

(ilO%)

chloroform

this

the dichloro

benzyltriethyl

'-' (method B) leads to results

above.

to test

to allow

is not

the

methods

since

of the hydroxyl

adducts are formed case

with

under

phase

and selenyl in low yield

the thallium ethoxide

method. The since

B-hydroxyselenides

advantageously alkylation

replace

at selenium

in this letter will be particularly useful in organic 11,19-25 10-18 are now readily available. and sulfides

the classical 12-16

(sulfur

method 22'25)

which

requires

followed

by

a two steps treatment

reaction

synthesis It should involving

of the resulting salt 12,14 and phenylthio in the phenylseleno

with bases. It should be particularly suitable 22,25 series for which the alkylation reaction is quite difficult.

4571

Entries

Yield in 2 X,(temp,time in hrs) X

Rl

CHCIJ/TIOEt 80(20", 24)

SeMe SeMe

H Me Me t-Bu

57(20", 28)

SeMe

Ph

65(20", 4 )

SPh

H

90(20", 22)

SMe

H

70(20", 2 1

SePh SePh

CHC13/KOH

80(20", 24)

42+(20",8) 60+(20",3)

62(20" , 3,5)

Ho,

-=‘ -i

X

H

Ott

CHC13/T10Et

CHC13/KOH

Rl

R2

SePh

H

H

74(20", 2,5)

64(20", 3 1

SeMe

H

H

70(20", 7.5)

51(20",2,5)

SPh

H

H

64(20", 24 1

67(20",4.5)

SePh

H

Ott

50(20", 24 1

SePh

Ott

H

55(20", 30 )

:

Ott-CH-CH?OH X

*

/O\

Ott-CH-CH2

CHC13/T10Et

CHC13/KOH

m

SePh

54(20', 30)

51+!20", 5 1

n

SeMe

73(20", 7 1

42?20",1,5)

+ The corresponding gem dichloro cyclopropane (Ccl2 instead 0 has

isolated i-t

in + 8% yield),

1-decene is also formed in + 10 %

yield,

been

4572

TYPICAL a)

EXPERIMENTS

Thallium

2-hydroxydecane solid and

usual

(0.5 mmol,

(TlCl) begins

the

(2.8 mmol,

ethoxide

resulting

work-up

is

suspension

b)

benzyl

is stirred

vigorously crude

yellow

liquid

in chloroform

chloride (0.5 mmol,

solution at 20°C

mixture which

After

to a solution

(4 ml.).

stirring

over

preparative

ammonium

(5 ml) and 50% aqueous

brown

by

is added

celite.

layer

After

is

(50

is

hydroxide

for 2.5 hrs then extracted

is distilled

under

purified

P.L.C.

by

References

l-methylseleno

a few seconds,

chromatography

mg)

the

The crude mixture

added

126 mg), chloroform

of potassium

of

a white

for 7.5 hrs at 20°C, ether is added

leading to 70% yield of 1,2-oxidodecene

2-hydroxydecane

the

ml)

is filtered

purified

10/90),

Triethyl

126 mg)

to precipitate.

ether-pentane

1-methylseleno

0.4

reduced

affording

(P.L.C.,

Merck,

to

a

mixture

containing

(2.5 mmol, 300 mg), CH2C12 The two phase solution

with ether.

51%

Si02,

after

(rf 0.52).

(2.5 ml).

pressure

obtained

(15mm yield

After usual work up Hg) of

and

affords

a

1,2-oxydodecene.

and notes

1) D. Labar, J.L. Laboureur, and A. Krief, Tetrahedron Lett., 983 (1982). 2) J.L. Laboureur and A. Krief, Tetrahedron Lett., 2713 (1984) 3) H. Nishiyama, T. Kitajima, A. Yamamoto and K. Itoh, JCS Chem. Comm., 1232 (1982). 4) A. McKillop, unpublished results, we thank Prof. McKillop for providing us at the beginning of the work, with his result on the cyclopropanation of olefins with Thallium ethoxide in chloroform. 5) a) C.M. Hall, Synth. Comm., 1, 121 (1972) ; b) V.I. Shcherbakov, S.F. Zhil'tsov Zhur. Obsch. Khim, 40, 2046 (1970). 6) E.V. Dehmlow, Angew Chem. Int; ed., Engl, 13, 170 (1974). 7) M. Makosza, Pure and Appl. Chem., 43, 439 (1975). 8) M. Makosza, "Naked anions-phase transfer" conference paper of the international workshop on Modern Synthetic Methods, 7 (1976). Interlaken, Switzerland. Published by Schwerzerischer Chemiker Verband, Zurich. 9) W.E. Keller "Compendium of phase-transfer Reactions and Related Synthetic Methods" (1979). Fluka AG. CH 9470 Buchs Switzerland. 10) D.L.J. Clive, Tetrahedron Lett., 2, 1049 (1978), report 50. 11) A. Krief, Tetrahedron, 2, 2531 (1980), report 94. 12) W. Dumont and A. Krief, Angew Chem. Int. ed., Engl, 14, 350 (1975). 13) D. Van Ende, W. Dumont, and A. Krief, Angew Chem. Int. ed., Engl, Ifl, 700 (1975). 14) A.M. Leonard-Coppens and A. Krief, Tetrahedron Lett., 3227 (1976). 15) D. Labar and A. Krief, J.C.S. Chem. Comm., 564 (1982). 16) D. Labar, A. Krief, and L. Hevesi, Tetrahedron Lett., 3967 (1978). 17) T. Hori and K.B. Sharpless, J. Org. Chem., 5, 1689 (1978). 18) H.J. Reich, S.W. Wollowitz, J.E. Trend, F. Chow, and D.F. Wendelborn, J. Org. Chem., 43, 1697 (1978). 19) E.J. Corey and D. Seebach, J. Org. Chem., 31, 4097 (1966). 20) J. Peterson, J. Org. Chem.. 32, 1717 (1967). 21) D. Seebach, N. Meyer, and A.K. Beck, Justus Liebig's, Ann. Chem., 846 (1977) and references cited. 22) A. Anciaux, A. Eman, W. Dumont, and A. Krief, Tetrahedron Lett., 1617 (1975). 23) J.N. Denis, W. Dumont, and A. Krief, Tetrahedron Lett., 4111 (1979). 24) T.M. Dolak, and T.A. Bryson, Tetrahedron Lett., 1961 (1977). 25) J.R. Shanklin, C.R. Johnson, J. Ollinger, and R.M. Coates, J. Amer. Chem. Sot., 95, 3429 (1973). ACKNOWLEDGMENT The authors Scientifique dans them (J.L.L.I.

acknowledge the “Institut 1 ‘Industrie et 1 ‘Agriculture”

(Received

27

in

UK

June

1984)

pour 1 ‘encouragement de la II.R.S.I.A.1 for a fellowship

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