Facile route to 1-phosphoryl- and 1-sulfonyl-1,3-dienes via palladium-catalyzed elimination of allylic acetates

Tetrahedron Letters,Vo1.25,No.SO,pp 5719-5722,1984 Printed in Great Britain

FACILE

ROUTE TO l-PHOSPHORYL- AND l-SULFONYL-1,3-DIENES ELIMINATION OF ALLYLIC ACETATES

VIA PALLADIUM-CATALYZED

BjGrn Akermark*, Jan-E. Nystrb'm, Tobias Rein, and Jan-E. B&kvall*, of Organic Chemistry, Royal Institute of Technology, S-100 44 STOCKHOLM,

Department

Department

oo40-4039/84 $3.00 + .OO 01984 Pergamon Press Ltd.

Paul Helquist*sl and Robert Aslanian State University of New York, Stony Brook,

of Chemistry,

Sweden

New York 11794-3400

U.S.A.

Abstract: The palladium(II)-catalyzed chloroacetoxylation of 1,3-dienes is employed to prepare 1-chloro-4-acetoxy-2-alkenes which are then transformed into 1-phosphoryl- or lsulfonyl-4-acetoxy-2-alkenes respectively. Elimination of acetate is promoted by palladium(O)-catalysis or by sodium hydride, producing the useful 1-phosphoryl- or lsulfonyl-1,3-dienes. Metal-catalyzed as important

nucleophilic

synthetic

the transformation 4-substituted

of allylic

general

reactions

into 1,3-dienes

by elimination

2 are readily available

chloroacetoxylation-nucleophilic

route to specifically

us to develop

both of which

efficient

are interesting

The five chloroacetates

are now recognized

classes

general

substitution

of the acetate.3

sequence

1,3-dienes 5

Because

(via L),4

a

is at hand (eq. 1).

studies of this basic strategy which, to date,

routes to l-phosphoryl-

of synthetic

5-8 were prepared

may also effect

from simple dienes 1 by a

I-functionalized

In this account, we report our exploratory has permitted

of allylic acetates

Recent work has shown that metal catalysts

acetates

1-acetoxy-2-alkenes

palladium(II)-catalyzed potentially

substitution

reactions. 2

and 1-sulfonyl-1,3-dienes,

intermediates.5-6

from the corresponding

1,3-dienes

as described

previously.4

The chloroacetaTey5-7 were smoothly transformed into the phosphoryl acetates _9-11 _employing an Arbuzov reaction, whereas the chloroacetate 8 failed to react satiSfaCtorilY under a wide range of conditions. The sulfonyl acetates -12-15 were prepared in high yield by utilizing a mild Palladium(O)-catalyzed substitution of the allylic chloro group with sodium benzenesulfinate. configuration.

The double Furthermore,

a occurs with complete

bond in the intermediate the Pd(O)-catalyzed

retention

compounds -9-15 is formed with retention of the chloro group in

substitution

at carbon.4a*c.d

The conversion treatment

of the intermediates -9-15 to the dienes -16-22 is generally achieved by with a weak base, e.g. triethylamine, in combination with a palladium(O)-catalyst

acetonitrile method

as solvent.

The phosphoryl

dienes -16-18 were

(Table).

5719

isolated

in good yield

using this

and

of

5720

Table

Chloroacetate

Conditionsa

AC0--P-JC’

A,5h

,,,&'I

AcOW

POlOEtl2 ;

A,0/x_L~~oHt~2

A,l9h 8

AC0

Conditionsa

Intermediate,yieldb(E/Z)

70(9/i)

C,llhc

70d(3/l)

C,5h

Diene products,

wPO(OEt12

Cl

A,l9h

-Cl , .?l.d -ia

B,3Omin

11

AcOJ==Lc,0Et12 11

74(1/9)

ACO-Qm

a7f(9/i)

POlOEt)Z

C,30min

92d*g (3/l)

C,3h

AcOA

B,ah

1A

iV!

AC+"

53020/l)

&SO2Ph

&i/2)

z!J

D,lOh

76m(99/l)

AcO+S02Ph

B,2h1

C,4h

rs*.s*,-15

lS'.S",-a

AcO’bVC’

2_2

B,2h1

71rn(99/l)

D,2h

lE,El-22

C,5h

2_2

D,96h

IE.El-22

,S:R",-ez

a) A: P(OEt13,

1,l eq; NaI, 10 mol%;

20°C. C: Et3N, 2 eq; Pd(PPh3)4, b) All yields

c) THF, 4O'C. d) Contains adducts

-23 (24%). j) -24 is also formed excess

In some cases direct

4 eq; Pd(PPh314,

10 mol%; CH3CN,

isolated by chromatography

10% of the 3-methyl

CH2=CR-CR(S02Ph)-CH20Ac

m) Diastereomeric

125'C. B: PhS02Na,

5 awl%; Diphos,

refer to pure products

79(30/l)

18 wS02Ph

C,8h

aih(i/9)

S02Ph

90d(2/3)

C,72he

Aco&S%Ph ACO~C,

7ad(i/i)

17 D,3h

z

80(4/i)

&WOEti2

?_o

2--c

yieldbWZ)

regioisomer.

are also formed:

75(4/l) 80

3 mol%; THF/DMSO

75'C. D: NaH, or Kugelrohr

e> Pd(PPh314,

a5

distillation.

10 mol%.

f)-h)

1,2-

f) 9%, g) 6%, h) 13%. i) The main product

(14%). k) -21 is also formed

9/l,

I,2 eq; THF, 45'C.

(11%). 1) Pd(PPh3j4,

is

5 mol%; 50°C.

90%. treatment

of the intermediate

phosphoryl-

or sulfonylacetate

with

sodium hydride

gave a better result. For instance treatment of -10 with sodium hydride (1.2. eq) in THF at 45O for 3 hrs gives 17 (E/Z = 2/3) in 90% isolated yield. The sodium hydride method (II) is also preferred (2% of (E,Z)-22

in the synthesis

(HPLC).

In contrast,

of (E,E)-E,

which was isolated

the Pd(O)-catalyzed

elimination

in 85% yield

and contained

(method C) gives -20% of

(E,Z)-22 - best conditions for the elimination of acetate from 12-14 were Pd(O)-catalysis and The -* -triethylamine in acetonitrile(C). The use of strong base frequently led to polymerization of the

5721

product

Other by-products

dienes.

Elimination

Pd(O)-catalysis. major

The expected

diene product.

NMR and HPLC data indicate

for example

were also formed,

from -13 resulted

in formation

dimers from 19,

of the rearranged

presumably

by

isomer -23 as the

product -20 was formed to a minor extent.

that the dienes are generally

mixtures

of E/Z isomers.

The

unsubstituted

dienes -16 and 19 as well as the disubstituted -18 and 21 are predominantly the Eisomers, while isoprene derived compounds -17 and 20 are an essentially equal mixture of the E and By the Z isomers.8e The formation of -21 was always accompanied by the double bond isomer -* 24 method, -24 became the major product, most likely via a-protonation Accordingly, it was observed that (E)- and (Z)-17 ally1 anion. - could be

of

use of the sodium hydride an intermediate converted

to -25 in good yield intermediates. The sodium hydride

by treatment

induced

Both -24 and 25 should be useful

with LDA.

from (S*,S*)-15 -

elimination

and (S*,R*)-15 -

synthetic

is noteworthy

as both

compared with 4 gave the same diene -22 but at very different rates, 2h for (S*,S*)-15 days for (S*,R*)-15, The result can be rationalized by considering the most stable rotamers of compounds

compounds -' 15 predominantly difference

In (S*,S*)-15 the proton and the acetoxy group that undergo elimination are syn to one another, whereas in (S*,R*)-15 The rate -- they are predominantly anti.

thu? indicates

The formation

that the 1,4-elimination

of mixtures

of isomers

is also true of the previously dienes_5d,e;6a,b;7,8.

developed

A comparison

largely upon the relative

selectivity

of the chloroacetoxylation

provide distinct

advantages.

is of course not specific syntheses

of l-phosphoryl-

with other methods

will depend

dienes

IS syn-stereoselective.

availability

studying

procedures

must be made on an individual

of the appropriate

and the potential

He are therefore

to the present

generality in a general

but

and l-sulfonyl-

substrates.

basis and

The

of the present methodology fashion

the synthesis

of

from I-substituted-4-acetoxy-2-alkenes

The corresponding

dienes,

which

3 including those with Nu= NR2, SR, OR, and SiR3. should be readily available by the methodoldogy described in this

Paper, have been well-documented Acknowledgements. Natural

Science

Research

Council

U- S. National Science Foundation administered

by the American

Scandinavian

Foundation,

Sweden.

Professor

as components

in Oiels-Alder

reactions.'

We are very grateful for the generous financial of Sweden,

the Swedish

Society

is gratefully

the Petroleum

(Grant No. 14337-ACl-C),

the latter for having provided

M. Julia

Board for Technical

(Grant No. CHE 8120466),

Chemical

acknowledged

support provided

a fellowship for supplying

Development,

Research

by the

the

Fund

and the Americanfor P.H. while on leave in data on the diene -, 22.

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