TetrahedronLetters,Vo1.22, No.

45, pp 4281 - 4282, 1981

Printed in Great Britain

0040-4039/81/434281-02$02.00/O
01981 Pergamon Press Ltd.

SYNTHESIS OF OPTICALLY ACTIVE PHEROMONES WITH AN EPOXY RING,

(+)-DISPARLURE AND THE SALTMARSH CATERPILLAR MOTH
PHEROMONE [(Z,Z)-3,6-c&-9,10-EPOXYHENEICOSADIENE]
Kenji Mori* and Takashi Ebata
Department of Agricultural Chemistry, The University of Tokyo,
Yayoi l-l-l, Bunkyo-ku, Tokyo 113, Japan
Abstract : (+)-Disparlure _2_and the saltmarsh caterpillar moth pheromone
enantiomers l-were synthesized and the stereochemistry of the naturally
occurring Lwas
shown to be 92, 105.
(Z&g)-3,6-cis-9,10-Epoxyheneicosadiene&was

identified by Hill and

Roelofs as one of the three components of the sex pheromone emitted by females
of the saltmarsh caterpillar moth, Estigmene acrea (Drury).1) Importance in
insect life of optically active epoxides such as juvenile hormones and disparlure_?_made us to synthesize both (95, 105) - and (9f3,lOs)-Lso

as to es-

tablish the stereochemistry of the natural pheromone.

As a model experiment, we first attempted a simple synthesis of (+)-disparlure A,

the pheromone of the gypsy moth (Porthetria ;1

dis p ar). 2r3)

Our stra-

tegy was to employ the Sharpless asymmetric epoxidation )

(k+z)
and the
coupling of an epoxy tosylate with lithium dialkylcuprate 5)as two key-reactions.

An acetylenic alcohol Awas

MeOH) to give (z)-5 (91.6% yield).

semi-hydrogenated (H2/Pd-BaSO4/quinoline/
This was epoxidized [Ti(Oi-Pr)4-diethyl L-

(+)-tartrate-t-BuOOH/CH2C12, -2O", 18 hr]')to (25, 3R)-z

-2.55' (c=2.43, CHCl,).')
CgHlg)2CuLi

(80.8% yield),[e]il

The corresponding tosylate zwas

(1.4eq) in ether at -20" for 3 hr to give (7$

reacted with (n8S)-(+)-disparlure

2 (47% yield after TLC purification), [a],21 + l.1 f 0.5O (c=2.3, CC14), identical with an authentic sample. 3)
For the synthesis of A, a triynol Awas

prepared from ethyl bromide and

propargyl alcohol in the conventional manner. This was hydrogenated (H2/P-2(23.7% yield after careful purification on a
Ni/H2N(CH2)2NH2-EtOH) 7) toA
Merck Lobar column).

Asymmetric epoxidation [Ti(Oi-Pr)4-diethyl L-(+)-tar-

trate-t-Bu00H/CH2C12, -20, 26hr14) ofc;Cyielded

(25, 3R)-& (54.8% yield

after chromatographic purification on a Merck Lobar column), [a],23-8.30(c=
0.964, CHC13)8).

The corresponding tosylate (25, 35)-z

was treated with

(n-C10H21)2CuLi (1.0 eq) in ether at -20" for 1.5 hr to give (9R, 105)-A
(43.8% yield after TLC purification),[e]230
+ 77.1, [e]24o + 42.9', [e]26o
+ ~O.O',[U]~~~ + 14.3'; CD As + 0.23 (205 nm). 9) Similarly, by employing
diethyl D-(-)-tartrate instead of L-(+)-isomer,Lafforded
(2R, 35)-E (60.3%
yield), [&Ii3 + 8.02O (c=1.16, CHC13).8) Treatment of the corresponding
4281

4282

/L

\\0

/.OH,-H

tOSylate (2E, 321-g

8Sb2_

2
l!a1230-43.3,

(7R,

(9S,lOR)-1

(9R,1OSbl_

&

R=H

(9R ,lOSbl_

R=Ts

with (n-ClOH2112CuLi gave (92, lOR)-1 (33,9% yield),

cJ-l240-33.3~,

[:@1260-20.8, [u1280-15.0~ CTAE-0.18

(205 nm).

Since the natural pheromoneexhibited negative ORD and CD curves, 10) (92,
lOF$-stereochemistry was assigned to the saltmarsh caterpillar moth pheromone.
Bioassay of the enantiomers is now under way by Prof. W.L. Roelofs.")

REFERENCES AND FOOTNOTES

1)
2)

3)
4)
5)
6)
7)
8)
9)

10)
11)

A.S. Hill and W.L. Roelofs, J. Chem. Ecol., in the press.

An independent synthesis of (+)-Lby a different route (asymmetric epoxidation-oxidation-Wittig reaction-hydrogenation) has recently been reported : B.E. Rossister, T. Katsuki and K.B. Sharpless, J. Am. Chem. Sot.,
103, 464 (1981).
For previous syntheses of (+)-- see, K. Mori "The Synthesis of Insect
Pheromones," pp 146-151 in J. ApSimon (ea.) "The Total Synthesis of
Natural Products, Vol. 4", John Wiley & Sons, New York (1981).
T. Katsuki and K.B. Sharpless, J. Am. Chem. Sot., _102, 5974 (1980).
G.H. Posner, "An Introduction to Synthesis Using Organocopper Reagents,"
Chapter 3, John Wiley & Sons, New York (1980).
This was highly optically pure as judged by the lH-NMR measurement of the
corresponding acetate (50 mg) in the presence of Eu(hfc)3 (60 mg) in Ccl4
[CH-0: racemate,
5.00 (m) and 5.30 (m); (22, 3R)-isomer, 6-4.99 (ml].
C.X. Brown and V.K. Ahuja, J.C.S. Chem. Comm., 553 (1973).
ion is known to give highly optically pure epoxides
Direct determination of the optical purity of &&
was not attempted due to the scarcity of the material.
lH-NMR 6 (lOOMHz,
1.78-2.42 (4H, m),

revealed the presence of three small signals at 6 123.77, 128.57 and

131.00 with intensities of about 6% of those of the major signals. This
im lies that the cis-trans isomeric purity of our synthetic&is
about 91
%P lOO-(6/2) x 33.
W.L. Roelofs, Personal communication to K.M. dated November 14, 1978.
We thank Professors W.L. Roelofs, K.B. Sharpless, and the late Dr. A.S.
Hill for exchange of informations. Our thanks are due to Drs. T. Umemura
and M. Horiba, Sumitomo Chemical Co., for ORD and CD measurements.
(Receivedin Japan 11 July 1981)