Concerning the reactivity of 1,2:3,4-diepoxides towards nucleophiles

Tetrahedron Letters,Vol.29,No.35,pp Printed in Great Britain

CONCERNING

THE REACTIVITY

OF 1,2:3.4-DIEPOXIDES

Thomas

Institut

fur Organische

0040-4039/88 $3.00 + .OO Perqamon Press plc

4405-4406,1988

TOWARDS

NUCLEOPHILES

Esser and Urs Sequin*

Chemie der Universitat,

CH-4056

St. Johanns-Ring

19,

Basel. Switzerland

Summary: anti-Benzenedioxide reacts with various nucleophiles to give the products resulting from the attack at both epoxy functions. With butyllithium, however. the formation of a product with a central epoxide is observed. This product is not the result of an epoxide migration but rather of the attack of the nucleophile at the double bond.

1,2:3,4-Diepoxides intermediates

in the

nucleophiles functions

has so far only

was observed.3

cyclopentane epoxide

('1)5 was

was obtained

obviously migration.

are of

formed

interest

synthesis

In

of

model compounds

allowed

to

in addition

the only

to this. Kozlov

the expected

opening

Independent

case where

amines.

substances

of one

natural

products'

of

the formation

a

of the two epoxy

product 3 with

2 and

such a

and as towards

that when anti-diepoxya central

3. This compound

the epoxides of

behavior

reaction

et a1.4 found

react with secondary to

for

substances. 2 Their

active

been studied marginally. contrast

by nucleophilic

This is

as

biologically

and subsequent central

epoxide

4 was epoxide

has been

described.

0

OH

HNR, -

0;"' *, d

1

2

In order

to

investigate

we treated

at all. 0-

independently

some

whether

compounds (5)6

was

either

rearrangement7

4

7

by

other, giving

nucleophilic

or by

A third possibility,

attack

attack at C(2) and the attack

type of reaction

of the

lead

secondary

epoxide

of

type 5.

migration nucleophile

4405

with

at C(4)

no

1.2:3,4-dinucleophiles.

reaction

when

double bond

or

could

butyllithium

was

in several

subsequent

(SN2'-reaction).

and subsequent

be

epoxy functions

Yet. 1 can be formed

simultaneous

of the

with

of the two

However,

was obtained.

C(3)

general

with various

amines.

to simple opening

products

at

is

class of substances

treated with

and S-nucleophiles

from each

this

of this

used. a single product 1 with a central ways:

"',N,$

6

When anti-benzenedioxide discerned

,,O."

3

5

epoxides,

+

+ '"'NS

Payne 8-10

rearrangement

of

4406 the allylic

alcohol

thus formed. would

lead to a product

with the butyl group cis to the epoxide. rearrangement

of the allylic

alcohol

with the same constitution

This third pathway

as 1 but

can here be ruled out, since the

would only occur in acidic milieu,

which was not used in

our experiments. The

way of formation

of this product 1

labelled

anti-benzenedioxide 11 but Altenbach and Vogel, carried

was investigated

This compound

the reduction

was

and 5. Thus, compound C(3) of 8. Kozlov's

labels were

The determination

exceptions8 consisting 36:55:6.

of

Therefore,

the corresponding of

NOE

of a central

epoxide

interesting

tried to

cuprates

contain

is

positions

spectra

with compound

of

-10 and

cis-

a unique case.

1

and

z

11

to

be

rather

by reaction

with methyllithium

the diadduct

case is again

in

one of

z

for H-C(4)

of and

where

of

a

ratio of

1 and

lo,

irradiation detected.

of

It is

an alkyllithium

the cis-product.

provided

by the Swiss National

AND NOTES

Uic Sgquin. Tetrahedron Lett. 3703 (1979). P. Weyerstahl. Klinkmiiller. H. Marschall, .- .

see e.g.

upon

no such NOE's were

those exceptions

to give predominantly

.----I-

-11 in

and trans-configurations

could be observed

of H-C(4);

REFERENCES

(i977).

in 2

at C(2) and not at

of 7 proved

vinyloxiranes

ACKNOWLEDGEMENT: Financial support of this work was generously Science Foundation (grant no. 2.438-0.84).

!. &;Ci;:

4 but rather

of isomers which - besides a few 9,lO trans-isomer. We obtained a product mixture

the

z weak NOE's

that our

C(4)-epimers,

trans-isomer

proved

irradiation

was

yield mixtures

the

1. the

both

at C(4)

of

gave a product

10

The reaction

known to

reacts with a vinyloxirane

:

1 and

thus still represents

configuration

prepare

predominantly

the cis-isomer

to note

relative

procedure

dibromocyclohexenedione

5

the

we

and for H-C(l) upon

compound

to the

of 8 with butyllithium

not in the expected

(2) with LiCu(Bu)2.

difference

respectively:

analogy

intermediate

Reaction

9

anti-benzenedioxide

with the aid of the deuterium in

2 must have been formed by attack of the nucleophile

observation

8

difficult.

prepared

of the

out with NaBD4 rather than with NaBH4.

2 where the two deuterium

H-C(l)

8.

Liebigs

Ann. Chem.

11572

W.-S. Tsang, G. W. Griffin, M. G. Horning, W. G. Stillwell, J. Org. Chem. 47, 5339 (1982). 4 N. S. Kozlov. L. S. Yakubovich, K. A. Zhavnerko, V. M. Prishchepenko, Zh. Org. Khim. 18. 2094 (1982) (J. Org. Chem. USSR (Engl. Transl.) 2, 1842 (1983)). All compounds are racemic; the formulae represent relative configurations only. H.-J. Altenbach, E. Schmidbauer, Angew. Chem. 85, 862 (1973); b) C. H. 65 a) E. Vogel, Foster, G. A. Berchtold. J. Org. Chem. 40, 3743 (1975). G. B. Pavne. J. Org. Chem. 27. 3819 (1962) : J. C. Saddler. P. L. Fuchs, J, Any. Chem. Sot. 103. 2112 (1981). Chem. Sot. 93, 30 46 (1971). 9 J. Staroscik, B. Rickborn, J. Am. 1 10 D. M. Wieland, C. R. Johnson. J. AIn. Chem. Sot. 93. 3047 (1971). 11 H.-J. Altenbach, H. Stegelmeier, E. Voge !l, Tetrahed ron Lett. 3333 (1978). 3

(Received in Germany 23 June 19881