New synthesis of the (3Z,6Z,9S,10R)-isomers of 9,10-Epoxy-3,6-henicosadiene and 9,10-epoxy-1,3,6-henicosatriene, pheromone components of the female fall webworm moth, Hyphantria cunea

Article abstract of DOI:10.1271/bbb.69.1007

(3Z,6Z,9S,10R)-9,10-Epoxy-3,6-henicosadiene (1) and (3Z,6Z,9S,10R)-9,10- epoxy-1,3,6-henicosatriene (5), pheromone components of the female fall webworm moth (Hyphantria cunea Drury), were synthesized by starting from (2S,3R)-2,3-epoxy-4-t-butyldimethylsi

Full text of DOI:10.1271/bbb.69.1007

Biosci. Biotechnol. Biochem., 69 (5), 1007–1013, 2005
New Synthesis of the (3Z,6Z,9S,10R)-Isomers of 9,10-Epoxy-3,6-henicosadiene
and 9,10-Epoxy-1,3,6-henicosatriene, Pheromone Components of the Female
*
Fall Webworm Moth, Hyphantria cunea
y
1
2;
Akira NAKANISHI and Kenji MORI
1Department of Applied Biological Chemistry, The University of Tokyo, Yayoi 1-1-1, Bunkyo-ku,
Tokyo 113-8657, Japan
2Insect Pheromone and Traps Division, Fuji Flavor Co., Ltd., Midorigaoka 3-5-8, Hamura-City,
Tokyo 205-8503, Japan
Received January 18, 2005; Accepted February 14, 2005
(3Z,6Z,9S,10R)-9,10-Epoxy-3,6-henicosadiene (1) and
(3Z,6Z,9S,10R)-9,10-epoxy-1,3,6-henicosatriene (5),
pheromone components 4 and 5 were subsequently
´
identified by Toth et al., and a mixture of 1–5 attracted
pheromone components of the female fall webworm
moth (Hyphantria cunea Drury), were synthesized by
starting from (2S,3R)-2,3-epoxy-4-t-butyldimethylsilyl-
oxy-1-butanol (8). Epoxide 8 was prepared by employ-
ing lipase-catalyzed asymmetric acetylation of (Æ)-8 as
the key optical resolution step.
H. cunea males.2) Later, Senda et al. found that a blend
of 1, 3 and 5 could attract H. cunea, and this blend has
been developed as a commercial lure for monitoring the
population of H. cunea.3)
The synthesis of (3Z,6Z,9S,10R)-9,10-epoxy-3,6-
henicosadiene (1) was first reported by Mori and Ebata
in 1986 by employing Sharpless asymmetric epoxidation
as the key step.4) Similarly, by employing the same
Key words: epoxide; Hyphantria cunea; lipase; phero-
mone; skipped diene
reaction,
(3Z,6Z,9S,10R)-9,10-epoxy-1,3,6-henicosa-
triene (5) and its lower homolog (4) were synthesized
in 1989.5) In these previous syntheses, the overall yield of
1 was 7% (10 steps),4) and that of 5 was 1.5% (12 steps).5)
Although there have been four additional syntheses of 1
or 5, none of them was efficient enough to furnish 1 and 5
in suitable quantity.6–9) We therefore undertook the
development of a more efficient route to secure 1 and 5,
this paper describing a new and more practical synthesis
of 1 and 5. It should be added that 3 is readily available
from linolenic acid [(9Z,12Z,15Z)-9,12,15-octadecatrie-
noic acid].
The fall webworm moth (Hyphantria cunea) is a
troublesome pest in Japan, where its larva attacks fruit
trees and ornamental trees such as grape, peach, pear,
apple, cherry, poplar and platan. Its female-produced
pheromone was first studied by Roelofs and his co-
workers, who identified three pheromone components 1–
3.1) A blend of 1–3 (Fig. 1), however, was biologically
inactive when tested against H. cunea. Two additional
Results and Discussion
Our key idea in exploiting the new synthesis of 1 is to
adopt epoxy-containing building block E (Scheme 1) as
the pivotal intermediate which can be prepared from
(ꢀ)-F by lipase-catalyzed asymmetric acetylation. Such
a chiral and non-racemic epoxy building block was first
utilized in pheromone synthesis by Brevet and Mori in
1992,10) and then extensively employed in our subse-
quent pheromone syntheses.11) In 2003, Muto and
Mori employed a t-butyldiphenylsilyl (TBDPS) version
[TBDPS instead of t-butyldimethylsilyl (TBS)] of E in
the syntheses of leucomalure12) and other epoxy pher-
omones.13)
Fig. 1. Structures of Components 1–5 of the Female Sex Pheromone
of the Fall Webworm Moth, Hyphantria cunea.
A mixture of 1,3 and 5 attracted the moth.
*
Pheromone Synthesis, Part 230. For Part 229, see Mori, K., Eur. J. Org. Chem., in press.
To whom correspondence should be addressed. Fax: +81-42-555-7920; E-mail: kjk-mori@arion.ocn.ne.jp
y

1008
A. NAKANISHI and K. MORI
Scheme 2. Preparation of Epoxy Building Block (2S,3R)-8.
Reagents: (a) 1.0 eq NaH, TBSCl, THF. (b) MCPBA, CH2Cl2 (2
steps, 81%). (c) lipase PS-C, CH2=CHOAc, Et2O, room temp., 3 h
[47% of (2R,3S)-8 (81% e.e.) and 49% of (2S,3R)-9 (84–87% e.e.)].
(d) K2CO3, MeOH (quant.). (e) C6H5COCl, C5H5N. (f) TBAF, THF
(2 steps, 96%).
Scheme 1. Retrosynthetic Analysis of 1.
Scheme 1 shows the retrosynthetic analysis of
(9S,10R)-1. Epoxide 1 can be prepared by coupling
epoxy tosylate A with lithium di(n-decyl)cuprate (B).
The carbon skeleton of A is to be constructed by
alkylating D with triflate C,12) triflate C being derived
from E.
The preparation of epoxy building block (2S,3R)-8 is
summarized in Scheme 2. Since TBS chloride is much
less expensive than TBDPS chloride, (Z)-2-butene-1,4-
diol (6) was converted to mono TBS ether 7. Epox-
idation of 7 with m-chloroperbenzoic acid (MCPBA)
furnished (ꢀ)-8 in an 82% yield. Lipase PS-C (Amano)
was chosen as the catalyst for the asymmetric acetyla-
tion of (ꢀ)-8 on the basis of our previous screening
experiment.12) Treatment of (ꢀ)-8 with vinyl acetate in
diethyl ether in the presence of lipase PS-C afforded
(2R,3S)-8 [47% yield based on (ꢀ)-8] and (2S,3R)-9
(49% yield). These stereochemical assignments were
made in analogy with those for the corresponding
TBDPS-protected compounds,12) and confirmed by sub-
sequent conversion of 9 to (9S,10R)-1 and 5. Their
enantiomeric purity, as determined by an HPLC analysis
of the derived 4-benzoyloxy-2,3-epoxy-1-butanol (80),
however, was not perfect: 81% e.e. for (2R,3S)-8 and
84–87% e.e. for (2S,3R)-9. In contrast, when we
employed the TBDPS protective group, each product
was almost enantiomerically pure (>99% e.e.).12,13) The
less bulky nature of the TBS group might have resulted
in less satisfactory chiral recognition by lipase PS-C.
Fortunately, however, final products 1 and 5 with 84–
87% e.e. had been found to be as effective attractants as
those with >99% e.e. according to the results of field
Scheme 3. Synthesis of (9S,10R)-1.
Reagents: (a) EtMgBr, Cu2Cl2, HCꢃCCH2Br, THF (55%). (b)
1.0 eq n-BuLi, 1.0 eq Tf2O, THF/HMPA, ꢁ78 ꢂC. (c) 1.2 eq n-
BuLi, 2.0 eq 11, THF, ꢁ78 ꢂC (2 steps, 67%). (d) H2, Lindlar Pd-
CaCO3-Pb2þ, cyclohexane (77%). (e) TBAF, THF (96%). (f) TsCl,
C5H5N. (g) (n-C10H21)2CuLi, Et2O (2 steps, 62%).
tests by scientists at Nitto Denko Co. (Dr. S. Senda,
personal communication to K.M.). Accordingly, we
proceeded to the next step, and (2S,3R)-9 of 84–87%
e.e. was converted to (2S,3R)-8 by a treatment with
potassium carbonate in methanol. The overall yield of
(2S,3R)-8 was 40% based on 6 (4 steps).
Scheme 3 summarizes the synthesis of one of the
target molecules, (9S,10R)-1. The side-chain diene part
of 1 was prepared from 1-butyne (10). The Grignard
reagent prepared from 10 and ethylmagnesium bromide
was alkylated with propargyl bromide in the presence of
copper(I) chloride to give 1,4-heptadiyne (11). Lithia-
tion of 11 was best carried out in THF at ꢁ78 ꢂC by
treating an excess (2.0 eq.) of 11 with n-butyllithium
(1.2 eq.) to give the corresponding lithium alkynide.

New Synthesis of the Pheromone Components of Hyphantria cunea
1009
Even a small excess of n-butyllithium abstracted a
proton at C-3 of 11, and gave a less clean product. The
alkynide was alkylated with triflate (2S,3R)-12 that had
been prepared from (2S,3R)-8. As reported previously,
this alkylation was successful only when triflate 12 was
employed,12) neither the corresponding tosylate nor
iodide giving an acceptable result.12) Resulting epoxy
diyne (2R,3S)-13 was obtained in a 67% yield, this being
semi-hydrogenated over Lindlar’s palladium catalyst to
give epoxy diene (2R,3S)-14. The TBS protective group
of 14 was then removed by a treatment with tetra(n-
butyl)ammonium fluoride (TBAF), and resulting alcohol
(2R,3S)-15 was tosylated to give tosylate (2R,3S)-16.
Finally, tosylate 16 was treated with lithium di(n-
decyl)cuprate to give (3Z,6Z,9S,10R)-9,10-epoxy-3,6-
henicosadiene (1). The overall yield of 1 was 12% based
on 6 (10 steps), this being considerably better than the
previous result (7%).4)
same manner as that described for the preparation of 11
to give 3,6-heptadiyn-1-ol (18). The hydroxy group of
18 was then protected as a trimethylsilyl (TMS) ether to
give 19, whose lithiate was alkylated with triflate 12 to
afford (2R,3S)-20, after removing the TMS group. Semi-
hydrogenation of 20 gave epoxy diene alcohol (2R,3S)-
21 which was treated with carbon tetrabromide and
triphenylphosphine to furnish bromide (2R,3S)-22. De-
hydrobromination of 22 was accomplished with potas-
sium t-butoxide in the presence of 18-crown-6 to give
triene (2R,3S)-23.14) After removing the TBS protective
group of 23, resulting alcohol 24 was converted to
corresponding tosylate (2R,3S)-25. Alkylation of 25
with lithium di(n-decyl)cuprate provided the desired
product,
(3Z,6Z,9S,10R)-9,10-epoxy-1,3,6-henicosa-
triene (5), in an 8.6% overall yield based on 6 (12
steps). In the case of the previous synthesis, the overall
yield was 1.5% (12 steps).
The synthesis of (9S,10R)-5 is shown in Scheme 4.
The side-chain triene part of 5 was prepared from 3-
butyn-1-ol (17), postponing the introduction of the
terminal olefin to a later stage of the synthesis. The
Grignard reagent prepared from 17 and 2 eq of ethyl-
magnesium bromide was alkylated with propargyl
bromide in the presence of copper (I) chloride in the
In conclusion, new and more efficient synthetic routes
were developed, leading to 1 and 5. Although the
present synthesis involves two low-temperature reac-
tions (8 ! 13 or 20 and 16 ! 1 or 25 ! 5) with
moderate yields, this new process may be useful in
synthesizing practical amounts of 1 and 5.
Experimental
IR data were measured with a Jasco FT/IR-410
1
spectrometer. H-NMR data were measured with a Jeol
JNM-EX 90A (90 MHz), Jeol JNM-AL300 (300 MHz),
Jeol JNM-LA400 (400 MHz) or Jeol JNM-LA500
(500 MHz) spectrometer (TMS at ꢀH ¼ 0:00 or CHCl3
at ꢀH ¼ 7:26 was used as the internal standard). MS data
were measured with a Jeol JMS-SX102 spectrometer,
and refractive index (nD) data were measured with an
Atago DMT-1 refractometer.
(2S,3R)-1-Acetoxy-4-t-butyldimethylsilyloxy-2,3-epoxy-
butane [(2S,3R)-9]. Lipase PS-C (50 mg) was added to a
solution of (ꢀ)-8 (2.00 g, 9.23 mmol) in Et2O (20 ml)
and vinyl acetate (1.5 ml) at room temperature (20–
24 ꢂC). After stirring for 3 h at room temperature, the
enzyme was filtered off, and the resulting filtrate was
concentrated in vacuo. The residue was purified by
chromatography (hexane/EtOAc, 5:1) to give (2R,3S)-8
(985 mg, 47%) and (2S,3R)-9 (1.22 g, 49%), both as
23
colorless oils. (2S,3R)-9: n2D3 ¼ 1:4414. ½ꢁꢄD ¼ ꢁ9:28
(c ¼ 1:04, CH2Cl2). IR ꢂmax (film) cmꢁ1: 1750 (s,
C=O), 1470 (m, Si–O), 1370 (m, C–O), 1230 (s, C–O),
1100 (s, Si–O), 1040 (m, C–O). 1H-NMR ꢀH (400 MHz,
CDCl3): 0.07 (3H, s, Si–Me), 0.08 (3H, s, Si–Me), 0.90
(9H, s, t-Bu), 2.10 (3H, s, Ac), 3.19 (1H, ddd, J ¼ 5:4,
4.8, 3.6 Hz, 3-H), 3.24 (1H, dt, J ¼ 7:4, 3.6 Hz, 2-H),
3.77 (1H, dd, J ¼ 11:8, 5.4 Hz, 4-Ha), 3.81 (1H, dd,
J ¼ 11:8, 4.8 Hz, 4-Hb), 4.05 (1H, dd, J ¼ 13:1, 7.4 Hz,
1-Ha), 4.35 (1H, dd, J ¼ 13:1, 3.6 Hz, 1-Hb). Anal.
Found: C, 55.22; H, 9.18%. Calcd. for C12H24O4Si: C,
55.35; H, 9.29%.
Scheme 4. Synthesis of (9S,10R)-5.
Reagents: (a) EtMgBr, Cu2Cl2, HCꢃCCH2Br, THF (55%). (b)
TMSCl, Et3N, DMAP, CH2Cl2 (93%). (c) 1.0 eq n-BuLi, 1.0 eq
Tf2O, THF/HMPA, ꢁ78 ꢂC. (d) i) 1.2 eq n-BuLi, 3.0 eq 19, THF,
ꢁ78 ꢂC. ii) K2CO3, MeOH [3 steps, 73% (average 60%)]. (e) H2,
Lindlar Pd-CaCO3-Pb2þ
, cyclohexane, cyclohexene (83%). (f)
CBr4, PPh3, CH2Cl2 (79%). (g) t-BuOK, 18-crown-6, hexane
(77%). (h) TBAF, THF (90%). (i) TsCl, C5H5N. (j) (n-C10H21)2-
CuLi, Et2O (2 steps, 65%).

1010
A. NAKANISHI and K. MORI
(2S,3R)-4-t-Butyldimethylsilyloxy-2,3-epoxy-1-butanol
dried over MgSO4, and concentrated in vacuo. The
residue was purified by chromatography (hexane/
AcOEt, 80:1) to give (2R,3S)-13 (3.77 g, 67%) as a
yellowish oil. IR ꢂmax (film) cmꢁ1: 2215 (w, CꢃC),
1470 (m, Si–C), 1390 (w, C–O), 1360 (w, C–O), 1100
[(2S,3R)-8]. K2CO3 (3.49 g, 25.2 mmol) was added to a
solution of (2S,3R)-9 (5.52 g, 19.4 mmol) in MeOH
(40 ml) at 0 ꢂC. The mixture was stirred for 1 h at 0 ꢂC,
quenched with saturated NH4Cl aq., and then extracted
with Et2O. The extract was successively washed with
water and brine, dried over MgSO4, and concentrated in
vacuo. The residue was purified by chromatography
(hexane/Et2O, 4:1) to give (2S,3R)-8 (4.22 g, quant.) as
1
(s, Si–O). H-NMR ꢀH (400 MHz, CDCl3): 0.08 (3H, s,
Si–Me), 0.09 (3H, s, Si–Me), 0.90 (9H, s, t-Bu), 1.12
(3H, t, J ¼ 7:5 Hz, 11-H), 2.17 (2H, tq, J ¼ 2:4, 7.5 Hz,
10-H), 2.32 (1H, ddt, J ¼ 17:5, 6.6, 2.4 Hz, 4-Ha), 2.57
(1H, ddt, J ¼ 17:5, 6.6, 2.4 Hz, 4-Hb), 3.07–3.12 (3H, m,
3-H, 7-H), 3.16 (1H, dt, J ¼ 4:1, 5.9 Hz, 2-H), 3.71 (1H,
dd, J ¼ 11:8, 5.9 Hz, 1-Ha), 3.81 (1H, dd, J ¼ 11:8,
5.9 Hz, 1-Hb). This compound was employed in the next
step without further purification.
23
a colorless oil. n2D3 ¼ 1:4481. ½ꢁꢄD ¼ ꢁ11:3 (c ¼ 1:01,
CH2Cl2) {lit.15) ½ꢁꢄD ¼ ꢁ10:5 (c ¼ 3, CH2Cl2)}. IR
ꢂmax (film) cmꢁ1: 3430 (br s, O–H), 1470 (m, Si–C),
1390 (m, C–O), 1360 (m, C–O), 1100 (s, Si–O), 1045
1
(m, C–O). H-NMR ꢀH (90 MHz, CDCl3): 0.09 (6H, s,
SiMe2), 0.90 (9H, s, t-Bu), 2.13 (1H, t, J ¼ 6:0 Hz, O–
H), 3.15–3.27 (2H, m, 2-H, 3-H), 3.72–3.91 (4H, m, 1-
1
(2R,3S,5Z,8Z)-1-t-Butyldimethylsilyloxy-2,3-epoxy-5,
8-undecadiene [(2R,3S)-14]. A solution of (2R,3S)-13
(3.43 g, 11.7 mmol) in cyclohexane (50 ml) was added to
an ice-cooled suspension of a Lindlar catalyst (5% Pd-
CaCO3-Pb2þ, 70.2 mg) in cyclohexane (70 ml) under
H2. After stirring for 2 h at room temperature, the
mixture was filtered through Celite, and the resulting
filtrate was concentrated in vacuo. The residue was
purified by chromatography (hexane/EtOAc, 100:1) to
give (2R,3S)-14 (2.69 g, 77%) as a colorless oil.
H, 4-H). The IR and H-NMR spectra were identical to
those reported.15)
Determination of the enantiomeric purity of (2S,3R)-
8. Benzoyl chloride (0.083 ml, 0.718 mmol) was added
to a stirred solution of (2S,3R)-8 (131 mg, 0.598 mmol)
in pyridine (0.3 ml) at 0 ꢂC. After stirring for 1 h at 0 ꢂC,
the reaction was quenched with water, and the mixture
was extracted with EtOAc. The extract was successively
washed with saturated CuSO4 aq., water and brine, dried
over MgSO4, and concentrated in vacuo. The residue
(204 mg) was dissolved in THF (5 ml), and then TBAF
(1.0 M in THF; 0.657 ml, 0.657 mmol) was added to the
solution at 0 ꢂC. After stirring for 30 min at 0 ꢂC, the
mixture was diluted with water, and extracted with
EtOAc. The resulting extract was successively washed
with water and brine, dried over MgSO4, and concen-
trated in vacuo. The residue was purified by chromatog-
raphy (hexane/EtOAc, 5:1) to give (2R,3S)-80 (120 mg,
96%) as colorless needles. HPLC analysis: column,
Chiralcel ODÒ 25 cm ꢅ 4:6 mm; eluent, hexane/2-prop-
anol (9:1); flow rate, 0.5 ml/min; UV detection at
254 nm; tR 30.8 min [93.4%, (2R,3S)-80], 34.8 min
[6.6%, (2S,3R)-80]. Enantiomeric purity of (2S,3R)-8:
87% e.e.
23
n1D9 ¼ 1:4610. ½ꢁꢄD ¼ þ1:52 (c ¼ 1:02, CHCl3). IR
ꢂmax (film) cmꢁ1: 1650 (w, C=C), 1460 (m, Si–O),
1
1390 (w, C–O), 1360 (w, C–O), 1100 (s, Si–O). H-
NMR ꢀH (400 MHz, CDCl3): 0.09 (3H, s, Si–Me), 0.10
(3H, s, Si–Me), 0.91 (9H, s, t-Bu), 0.98 (3H, t,
J ¼ 7:6 Hz, 11-H), 2.07 (2H, quint, J ¼ 7:6 Hz, 10-H),
2.23 (1H, dt, J ¼ 15:4, 6.6 Hz, 4-Ha), 2.42 (1H, dt,
J ¼ 15:4, 6.6 Hz, 4-Hb), 2.80 (2H, t, J ¼ 7:1 Hz, 7-H),
3.00 (1H, dt, J ¼ 4:4, 6.6 Hz, 3-H), 3.10 (1H, dt, J ¼
4:4, 5.6 Hz, 2-H), 3.76 (1H, dd, J ¼ 10:7, 5.6 Hz, 1-Ha),
3.80 (1H, dd, J ¼ 10:7, 5.6 Hz, 1-Hb), 5.27–5.55 (4H, m,
5-H, 6-H, 8-H, 9-H). Anal. Found: C, 68.67; H, 11.07%.
Calcd. for C17H32O2Si: C, 68.86; H, 10.88%.
(2R,3S,5Z,8Z)-2,3-Epoxy-5,8-undecadien-1-ol [(2R,
3S)-15]. TBAF (1.0 M in THF; 9.21 ml, 9.21 mmol)
was added to
a solution of (2R,3S)-14 (2.48 g,
(2R,3S)-1-t-Butyldimethylsilyloxy-2,3-epoxy-5,8-un-
decadiyne [(2R,3S)-13]. A solution of n-BuLi (1.59 M in
hexane, 12.2 ml, 19.4 mmol) was added dropwise to a
solution of (2S,3R)-8 (4.21 g, 19.3 mmol) in dry THF
(105 ml) at ꢁ78 ꢂC under argon. After stirring for 1 h at
ꢁ78 ꢂC, Tf2O (3.24 ml, 19.3 mmol) was added dropwise.
The mixture was stirred for 80 min at ꢁ78 ꢂC, and then a
solution of freshly prepared 1,4-heptadiynyllithium [a
solution of n-BuLi (1.59 M in hexane; 14.6 ml,
23.2 mmol) was added slowly to a solution of freshly
distilled 1,4-heptadiyne (11; 3.55 g, 38.6 mmol) and dry
THF (105 ml) at ꢁ78 ꢂC under argon, and then the
mixture was stirred for 3 h at ꢁ78 ꢂC] and dry HMPA
(17.5 ml) was added at ꢁ78 ꢂC. The mixture was stirred
for 1 h at ꢁ78 ꢂC, quenched with water, and then
extracted with Et2O. The extract was washed with brine,
8.37 mmol) in THF (70 ml) at 0 ꢂC. After stirring for
1 h at 0 ꢂC, the mixture was diluted with water and
extracted with EtOAc. The extract was successively
washed with water and brine, dried over MgSO4, and
concentrated in vacuo. The residue was purified by
chromatography (hexane/EtOAc, 5:1) to give (2R,3S)-
15 (1.46 g, 96%) as a slightly yellowish oil. nD16
¼
23
22
1:4821. ½ꢁꢄD ¼ þ8:69 (c ¼ 1:07, CHCl3) {lit.4) ½ꢁꢄD
¼
þ11:6 (c ¼ 0:84, CHCl3)}. IR ꢂmax (film) cmꢁ1: 3400
1
(br s, O–H), 1650 (w, C=C). H-NMR ꢀH (400 MHz,
CDCl3): 0.97 (3H, t, J ¼ 7:6 Hz, 11-H), 1.77 (1H, t,
J ¼ 5:2 Hz, O–H), 2.07 (2H, quint, J ¼ 7:6 Hz, 10-H),
2.27 (1H, dt, J ¼ 15:2, 7.6 Hz, 4-Ha), 2.48 (1H, dt,
J ¼ 15:2, 7.6 Hz, 4-Hb), 2.79 (2H, t, J ¼ 7:1 Hz, 7-H),
3.08 (1H, dt, J ¼ 4:3, 7.6 Hz, 3-H), 3.17 (1H, dt,
J ¼ 4:3, 6.6 Hz, 2-H), 3.73 (1H, ddd, J ¼ 12:0, 6.6,

New Synthesis of the Pheromone Components of Hyphantria cunea
1011
5.2 Hz, 1-Ha), 3.87 (1H, ddd, J ¼ 12:0, 6.6, 5.2 Hz, 1-
Hb), 5.25–5.55 (4H, m, 5-H, 6-H, 8-H, 9-H). 13C-NMR
ꢀC (100 MHz, CDCl3): 14.2, 20.6, 25.6, 26.4, 56.4, 56.6,
60.8, 123.6, 126.4, 131.2, 132.4. The IR and H-NMR
spectra were identical to those published elsewhere.4)
(1H, t, J ¼ 2:8 Hz, 7-H), 2.40 (2H, tt, J ¼ 6:8, 2.8 Hz,
2-H), 2.53 (2H, q, J ¼ 2:8 Hz, 5-H), 3.68 (2H, t, J ¼
6:8 Hz, 1-H). This compound was employed in the next
step without further purification.
1
(2R,3S)-1-t-Butyldimethylsilyloxy-2,3-epoxy-5,8-un-
decadiyn-1-ol [(2R,3S)-20]. A solution of n-BuLi
(1.56 M in hexane; 7.14 ml, 11.1 mmol) was added
dropwise to a solution of (2S,3R)-8 (2.43 g, 11.1 mmol)
in dry THF (60 ml) at ꢁ78 ꢂC under argon. After stirring
for 40 min at ꢁ78 ꢂC, Tf2O (1.86 ml, 11.1 mmol) was
added dropwise. The mixture was stirred for 40 min at
ꢁ78 ꢂC, and then a solution of freshly prepared 1-
trimethylsilyloxy-3,6-heptadiynyllithium [a solution of
n-BuLi (1.56 M in hexane; 8.53 ml, 13.3 mmol) was
added slowly to a solution of freshly distilled 19 (6.02 g,
33.4 mmol) and dry THF (60 ml) at ꢁ78 ꢂC under argon,
and then the mixture was stirred for 2 h at ꢁ78 ꢂC] and
dry HMPA (9.96 ml) were added at ꢁ78 ꢂC. The mixture
was stirred for 1 h at ꢁ78 ꢂC and then poured into
MeOH (120 ml). K2CO3 (3.07 g, 22.2 mmol) was added
to the mixture at room temperature. After stirring for 1 h
at room temperature, the mixture was concentrated in
vacuo, diluted with Et2O, successively washed with
water and brine, dried over MgSO4, and concentrated in
vacuo. The residue was purified by chromatography
(hexane/EtOAc, 5:1) to give (2R,3S)-20 (2.52 g, 73%)
as a yellowish oil. IR ꢂmax (film) cmꢁ1: 3420 (br s, O–
(3Z,6Z,9S,10R)-9,10-Epoxy-3,6-henicosadiene [(9S,
10R)-1]. p-Toluenesulfonyl chloride (1.21 g, 6.39 mmol)
was added to a stirred solution of (2R,3S)-15 (1.06 g,
5.81 mmol) in pyridine (4.2 ml) at 0 ꢂC. After stirring
overnight at 0 ꢂC, the mixture was poured into water,
and extracted with CH2Cl2. The extract was successive-
ly washed with saturated CuSO4 aq., water and brine,
dried over MgSO4, and concentrated in vacuo. The
residue (2.21 g) was dissolved in dry Et2O (30 ml) and
stirred at ꢁ40 ꢂC. The solution was added slowly to a
stirred suspension of lithium di(n-decyl)cuprate in Et2O
[n-decyllithium (0.92 M in Et2O; 24.7 ml, 22.7 mmol)
was added to a suspension of CuI (2.16 g, 11.3 mmol) in
dry Et2O (16 ml) at ꢁ40 ꢂC under argon, and then the
mixture was stirred for 3 h at ꢁ40 ꢂC.] at ꢁ40 ꢂC. After
stirring for 15 min at ꢁ40 ꢂC, the suspension was poured
into saturated NH4Cl aq., and extracted with Et2O. The
extract was successively washed with saturated NH4Cl
aq., water and brine, dried over MgSO4, and concen-
trated in vacuo. The residue was purified by chromatog-
raphy (hexane/EtOAc, 100:1) to give (9S,10R)-1
22
(1.11 g, 62%) as a colorless oil. n2D0 ¼ 1:4633. ½ꢁꢄD
¼
þ3:99 (c ¼ 1:65, CCl4). IR ꢂmax (film) cmꢁ1: 1650 (w,
C=C). 1H-NMR ꢀH (500 MHz, CDCl3): 0.90 (3H, t,
J ¼ 7:4 Hz, 1-H), 0.92 (3H, t, J ¼ 6:7 Hz, 21-H), 1.28–
1.50 (20H, m, 11-H, 12-H, 13-H, 14-H, 15-H, 16-H, 17-
H, 18-H, 19-H, 20-H), 1.99 (2H, quint, J ¼ 7:4 Hz, 2-
H), 2.16 (1H, dt, J ¼ 14:4, 6.2 Hz, 8-Ha), 2.37 (1H, dt,
J ¼ 14:4, 6.2 Hz, 8-Hb), 2.72–2.75 (1H, m, 10-H), 2.77
(2H, t, J ¼ 6:4 Hz, 5-H), 2.81 (1H, dt, J ¼ 4:0, 6.2 Hz,
9-H), 5.35–5.54 (4H, m, 3-H, 4-H, 6-H, 7-H). 13C-NMR
ꢀC (100 MHz, CDCl3): 14.1, 14.2, 20.6, 22.7, 25.7, 26.2,
26.6, 27.8, 29.3, 29.6, 31.9, 56.4, 57.2, 124.2, 126.7,
130.7, 132.2. Anal. Found: C, 78.20; H, 13.12%. Calcd.
for C21H38O: C, 77.72; H, 13.32%. FAB-HRMS m=z
(½M þ Hꢄþ): calcd. for C21H39O, 307.2995; found,
307.2993.
H), 2220 (w, CꢃC). H-NMR ꢀH (300 MHz, CDCl3):
1
0.09 (3H, s, Si–Me), 0.10 (3H, s, Si–Me), 0.91 (9H, s, t-
Bu), 1.78 (1H, br s, O–H), 2.30–2.37 (1H, m, 4-Ha), 2.45
(2H, tt, J ¼ 6:0, 1.8 Hz, 10-H), 2.53–2.60 (1H, m, 4-Hb),
3.10–3.21 (4H, m, 2-H, 3-H, 7-H), 3.71 (2H, t, J ¼
6:0 Hz, 11-H), 3.74 (1H, dd, J ¼ 11:7, 9.0 Hz, 1-Ha),
3.83 (1H, dd, J ¼ 11:7, 4.8 Hz, 1-Hb). This compound
was employed in the next step without further purifica-
tion.
(2R,3S,5Z,8Z)-1-t-Butyldimethylsilyloxy-2,3-epoxy-5,
8-undecadien-11-ol [(2R,3S)-21]. A solution of (2R,3S)-
20 (2.52 g, 8.14 mmol) and cyclohexene (4.12 ml,
40.8 mmol) in cyclohexane (24 ml) was added to an
ice-cooled suspension of the Lindlar catalyst (5% Pd-
CaCO3-Pb2þ, 47.0 mg) in cyclohexane (47 ml) under
H2. The addition of cyclohexene prevented over-reduc-
tion. After stirring for 4 h at room temperature, the
mixture was filtered through Celite, and the resulting
filtrate was concentrated in vacuo. The residue was
purified by chromatography (hexane/EtOAc, 50:1) to
1-Trimethylsilyloxy-3,6-heptadiyne [19]. Triethyl-
amine (9.37 ml, 67.2 mmol), chlorotrimethylsilane
(6.80 ml, 32.2 mmol) and DMAP (328 mg, 2.69 mmol)
were added to a solution of 18 (2.91 g, 26.9 mmol) in dry
CH2Cl2 (60 ml) at 0 ꢂC. After stirring for 30 min at 0 ꢂC,
the mixture was poured into water and extracted with
CH2Cl2. The resulting extract was successively washed
with water and brine, dried over MgSO4, and concen-
trated in vacuo. The residue was purified by chromatog-
raphy (pentane/Et2O, 100:1) to give 19 (4.45 g, 92%) as
a yellowish oil. Bp 81 ꢂC at 7.0 Torr. n2D5 ¼ 1:4510. IR
ꢂmax (film) cmꢁ1: 3300 (s, CꢃCH), 2130 (w, CꢃC),
1420 (w, Si–C), 1250 (s, Si–C), 1100 (s, Si–O). 1H-
NMR ꢀH (400 MHz, CDCl3): 0.13 (9H, s, Si–Me3), 2.06
give (2R,3S)-21 (2.12 g, 83%) as a colorless oil. nD24
¼
24
1:4721, ½ꢁꢄD ¼ ꢁ5:12 (c ¼ 1:00, CHCl3). IR ꢂmax
(film) cmꢁ1: 3420 (br s, O–H), 1650 (w, C=C), 1470
(m, Si–C), 1390 (m, C–O), 1360 (m, C–O), 1100 (s, Si–
1
O). H-NMR ꢀH (500 MHz, CDCl3): 0.09 (3H, s, Si–
Me), 0.08 (3H, s, Si–Me), 0.89 (9H, s, t-Bu), 1.74 (1H,
br s, O–H), 2.23 (1H, dt, J ¼ 14:7, 6.7 Hz, 4-Ha), 2.28–
2.42 (3H, m, 4-Hb, 10-H), 2.83 (2H, m, 7-H), 2.98 (1H,
dt, J ¼ 4:9, 6.7 Hz, 3-H), 3.08 (1H, dt, J ¼ 4:9, 5.8 Hz,

1012
A. NAKANISHI and K. MORI
2-H), 3.63 (2H, t, J ¼ 7:0 Hz, 11-H), 3.75 (1H, dd,
J ¼ 11:6, 5.8 Hz, 1-Ha), 3.78 (1H, dd, J ¼ 11:6, 5.8 Hz,
1-Hb), 5.38–5.53 (4H, m, 5-H, 6-H, 8-H, 9-H). 13C-
NMR ꢀC (125 Hz, CDCl3): ꢁ5:5, ꢁ5:4, 18.1, 25.7, 26.2,
30.7, 55.8, 56.8, 61.4, 61.8, 124.2, 126.0, 130.0, 130.4.
Anal. Found: C, 71.52; H, 11.48%. Calcd. for C17H32O3:
C, 71.79; H, 11.34%.
55.9, 56.9, 61.5, 117.7, 124.7, 129.5, 129.8, 130.0,
131.7. Anal. Found: C, 69.42; H, 10.20%. Calcd. for
C17H30O2Si: C, 69.33; H, 10.27%.
(2R,3S,5Z,8Z)-2,3-Epoxy-5,8,10-undecatrien-1-ol
[(2R,3S)-24]. TBAF (1.0 M in THF; 0.241 ml, 0.241
mmol) was added to a solution of (2R,3S)-23 (59.4 mg,
0.201 mmol) in THF (2.0 ml) at 0 ꢂC. After stirring for
2 h at 0 ꢂC, the mixture was diluted with water and
extracted with EtOAc. The extract was successively
washed with water and brine, dried over MgSO4, and
concentrated in vacuo. The residue was purified by
chromatography (hexane/EtOAc, 5:1) to give (2R,3S)-
24 (32.5 mg, 90%) as a colorless oil. n2D4 ¼ 1:4981.
(2R,3S,5Z,8Z)-11-Bromo-1-t-butyldimethylsilyloxy-2,
3-epoxy-5,8-undecadiene [(2R,3S)-22]. Carbon tetrabro-
mide (2.22 g, 6.70 mmol) and triphenylphosphine
(1.76 g, 6.70 mmol) were added to a solution of
(2R,3S)-21 (1.91 g, 6.09 mmol) in CH2Cl2 (40 ml) at
0 ꢂC. After stirring overnight at 0 ꢂC, the mixture was
diluted with pentane. The mixture was filtered through
Celite, and the resulting filtrate was concentrated in
vacuo. The residue was purified by chromatography
(hexane/EtOAc, 100:1) to give (2R,3S)-22 (1.81 g, 79%)
24
18
½ꢁꢄD ¼ þ5:09 (c ¼ 0:93, CHCl3) {lit.5) ½ꢁꢄD ¼ þ6:20
(c ¼ 1:66, CHCl3)}. IR ꢂmax(film) cmꢁ1: 3410 (br s, O–
1
H), 1640 (w, C=C). H-NMR ꢀH (500 MHz, CDCl3):
1.81 (1H, br s, O–H), 2.28 (1H, dt, J ¼ 15:0, 6.7 Hz, 4-
Ha), 2.47 (1H, dt, J ¼ 15:0, 6.7 Hz, 4-Hb), 2.95 (2H, t,
J ¼ 7:5 Hz, 7-H), 3.07 (1H, dt, J ¼ 4:3, 6.7 Hz, 3-H),
3.17 (1H, dt, J ¼ 4:3, 6.7 Hz, 2-H), 3.73 (1H, dd,
J ¼ 12:2, 6.7 Hz, 1-Ha), 3.86 (1H, dd, J ¼ 12:2, 6.7 Hz,
1-Hb), 5.14 (1H, d, J ¼ 10:1 Hz, 11-Ha), 5.22 (1H, d,
J ¼ 16:8 Hz, 11-Hb), 5.39 (1H, dt, J ¼ 11:0, 7.5 Hz, 8-
H), 5.45–5.56 (2H, m, 5-H, 6-H), 6.03 (1H, t,
J ¼ 11:0 Hz, 9-H), 6.64 (1H, dddd, J ¼ 16:8, 11.0,
10.1, 0.9 Hz, 10-H). 13C-NMR ꢀC (125 MHz, CDCl3):
26.2, 26.4, 56.3, 56.6, 60.7, 117.8, 124.4, 129.59,
129.64, 130.3, 131.8. The IR and 1H-NMR spectra were
identical to those published.5)
22
as a yellowish oil. n2D3 ¼ 1:4509. ½ꢁꢄD ¼ ꢁ0:97 (c ¼
1:02, CHCl3). IR ꢂmax (film) cmꢁ1: 1650 (w, C=C),
1470 (w, Si–C), 1390 (w, C–O), 1360 (w, C–O), 1260 (s,
C–Br), 1100 (s, Si–O). 1H-NMR ꢀH (500 MHz, CDCl3):
0.07 (3H, s, Si–Me), 0.08 (3H, s, Si–Me), 0.89 (9H, s, t-
Bu), 2.22 (1H, dt, J ¼ 14:7, 6.1 Hz, 4-Ha), 2.37 (1H, dt,
J ¼ 14:7, 6.1 Hz, 4-Hb), 2.62 (2H, q, J ¼ 7:0 Hz, 10-H),
2.80 (2H, t, J ¼ 6:1 Hz, 7-H), 2.97 (1H, dt, J ¼ 4:3,
6.1 Hz, 3-H), 3.06 (1H, dt, J ¼ 4:3, 5.5 Hz, 2-H), 3.35
(2H, t, J ¼ 7:0 Hz, 11-H), 3.75 (2H, d, J ¼ 5:5 Hz, 1-H),
5.36–5.52 (4H, m, 5-H, 6-H, 8-H, 9-H). 13C-NMR ꢀC
(125 MHz, CDCl3): ꢁ5:4, ꢁ5:3, 18.2, 25.8, 26.3, 30.7,
32.1, 55.7, 56.7, 61.4, 124.6, 126.6, 130.0, 130.4. Anal.
Found: C, 54.68; H, 8.17%. Calcd. for C17H31O2BrSi: C,
54.39; H, 8.32%.
(3Z,6Z ,9S,10R)-9,10-Epoxy-1,3,6-henicosatriene
[(9S,10R)-5]. p-Toluenesulfonyl chloride (51.2 mg,
0.269 mmol) was added to a solution of (2R,3S)-24
(36.2 mg, 0.201 mmol) in pyridine (1.0 ml) and CH2Cl2
(1.0 ml) at 0 ꢂC. After stirring overnight at 0 ꢂC, the
mixture was poured into water and extracted with
CH2Cl2. The extract was successively washed with
saturated CuSO4 aq., water and brine, dried over
MgSO4, and concentrated in vacuo. The residue
(70.3 mg) was dissolved in dry Et2O (1.0 ml) and stirred
at ꢁ40 ꢂC. This solution was added slowly to a
suspension of lithium di(n-decyl)cuprate in Et2O [n-
decyllithium (1.07 M in Et2O; 0.632 ml, 0.676 mmol)
was added to a suspension of CuI (65.3 mg, 0.342 mmol)
in dry Et2O (1.0 ml) at ꢁ45 ꢂC under argon, and then the
mixture was stirred for 3 h at ꢁ45 ꢂC] at ꢁ45 ꢂC. After
stirring for 15 min at ꢁ45 ꢂC, the suspension was poured
into saturated NH4Cl aq. and extracted with Et2O. The
extract was successively washed with saturated NH4Cl
aq., water and brine, dried over MgSO4, and concen-
trated in vacuo. The residue was purified by chromatog-
(2R,3S,5Z,8Z)-1-t-Butyldimethylsilyloxy-2,3-epoxy-5,
8,10-undecatriene [(2R,3S)-23]. Potassium t-butoxide
(44.9 mg, 0.400 mmol) and 18-crown-6 (7.0 mg, 0.027
mmol) were added to a solution of (2R,3S)-22 (100 mg,
0.267 mmol) in hexane (2.6 ml) at ꢁ40 ꢂC. After stirring
for 3 h at ꢁ20 ꢂC, the mixture was poured into saturated
NH4Cl aq. and extracted with Et2O. The extract was
washed with brine, dried over MgSO4, and concentrated
in vacuo. The residue was purified by chromatography
(hexane/EtOAc, 200:1) to give (2R,3S)-23 (61.0 mg,
23
77%) as a yellowish oil. n2D2 ¼ 1:4781. ½ꢁꢄD ¼ ꢁ2:05
(c ¼ 1:10, CHCl3). IR ꢂmax (film) cmꢁ1: 1640 (w,
C=C), 1470 (w, Si–C), 1390 (w, C–O), 1100 (s, Si–O),
1000 (m, C=C), 910 (m, C=C). 1H-NMR ꢀH (300 MHz,
CDCl3): 0.06 (3H, s, Si–Me), 0.08 (3H, s, Si–Me), 0.89
(9H, s, t-Bu), 2.24 (1H, dt, J ¼ 14:4, 6.4 Hz, 4-Ha), 2.41
(1H, dt, J ¼ 14:4, 6.4 Hz, 4-Hb), 2.95 (2H, t, J ¼ 6:5 Hz,
7-H), 3.00 (1H, dt, J ¼ 4:5, 6.4 Hz, 3-H), 3.10 (1H, dt,
J ¼ 4:5, 6.4 Hz, 2-H), 3.77 (2H, d, J ¼ 6:4 Hz, 1-H),
5.13 (1H, d, J ¼ 10:2 Hz, 11-Ha), 5.21 (1H, d,
J ¼ 16:8 Hz, 11-Hb), 5.35–5.58 (3H, m, 5-H, 6-H, 8-
H), 6.02 (1H, t, J ¼ 11:1 Hz, 9-H), 6.64 (1H, dddd,
J ¼ 16:8, 11.1, 10.2, 1.2 Hz, 10-H). 13C-NMR ꢀC
(75 MHz, CDCl3): ꢁ5:4, ꢁ5:3, 18.2, 25.8, 26.2, 26.4,
raphy (hexane/EtOAc, 100:1) to give (9S,10R)-5
21
(40.0 mg, 65%) as a colorless oil. n1D5 ¼ 1:4841. ½ꢁꢄD
¼
ꢁ0:38 (c ¼ 1:04, CHCl3). IR ꢂmax (film) cmꢁ1: 1630 (w,
C=C). 1H-NMR ꢀH (500 MHz, CDCl3): 0.88 (3H, t,
J ¼ 7:3 Hz, 21-H), 1.26–1.54 (20H, m, 11-H, 12-H, 13-
H, 14-H, 15-H, 16-H, 17-H, 18-H, 19-H, 20-H), 2.24

New Synthesis of the Pheromone Components of Hyphantria cunea
1013
(3Z,6Z)-cis-9,10-epoxy-1,3,6-icosatriene, the new pher-
omone components of Hyphantria cunea. Liebigs Ann.
Chem., 453–457 (1989).
(1H, dt, J ¼ 14:4, 6.1 Hz, 8-Ha), 2.40 (1H, dt, J ¼ 14:4,
6.1 Hz, 8-Hb), 2.91–2.98 (4H, m, 5-H, 9-H, 10-H), 5.13
(1H, d, J ¼ 10:7 Hz, 1-Ha), 5.22 (1H, d, J ¼ 16:8 Hz, 1-
Hb), 5.41 (1H, dt, J ¼ 10:5, 8.0 Hz, 4-H), 5.46–5.55
(2H, m, 6-H, 7-H), 6.03 (1H, t, J ¼ 10:5 Hz, 3-H), 6.65
(1H, ddd, J ¼ 16:8, 10.7, 10.5 Hz, 2-H). 13C-NMR ꢀC
(100 MHz, CDCl3): 14.1, 22.7, 26.2, 26.6, 27.8, 29.3,
29.6, 31.9, 56.3, 57.2, 117.7, 124.8, 129.7, 129.8, 130.0,
131.8. Anal. Found: C, 82.71; H, 12.04%. Calcd. for
C21H36O: C, 82.83; H, 11.92%. FAB-HRMS m=z
(½M þ Hꢄþ): calcd. for C21H37O, 305.2844; found,
305.2849.
6) Bell, T. W., and Ciaccio, J. A., Alkylative epoxide
rearrangement. A stereospecific approach to chiral
epoxide pheromone. J. Org. Chem., 58, 5153–5162
(1993).
7) Yadav, J. S., Valli, M. Y., and Prasad, A. R., Total
synthesis of enantiomers of (3Z,6Z)-cis-9,10-epoxy-
1,3,6-henicosatriene—the pheromonal component of
Diacrisia obliqua. Tetrahedron, 54, 7551–7562 (1998).
8) Zhang, Z.-B., Wang, Z.-M., Wang, Y.-X., Liu, H.-Q.,
Lei, G.-X., and Shi, M., A facile synthetic method for
chiral 1,2-epoxides and the total synthesis of chiral
pheromone epoxides. Tetrahedron: Asymmetry, 10, 837–
840 (1999).
Acknowledgments
9) Yadav, J. S., Valli, M. Y., and Prasad, A. R., Isolation,
identification, synthesis, and bioefficacy of female
Diacrisia obliqua (Arctiidae) sex pheromone blend. An
Indian agricultural pest. Pure Appl. Chem., 73, 1157–
1162 (2001).
10) Brevet, J.-L., and Mori, K., Enzymatic preparation of
(2S,3R)-4-acetoxy-2,3-epoxybutan-1-ol and its conver-
sion to the epoxy pheromones of the gypsy moth and the
ruby tiger moth. Synthesis, 1007–1012 (1992).
11) Mori, K., Enantioselective synthesis in natural product
chemistry—a personal account—. J. Synth. Org. Chem.
Jpn., 53, 952–962 (1995).
12) Muto, S., and Mori, K., Synthesis of all four stereo-
isomers of Leucomalure, components of the female sex
pheromone of the satin moth, Leucoma salicis. Eur. J.
Org. Chem., 1300–1307 (2003).
13) Muto, S., and Mori, K., Synthesis of the four components
of the female sex pheromone of the painted apple moth,
Teia anartoides. Biosci. Biotechnol. Biochem., 67, 1559–
1567 (2003).
We thank Dr. S. Senda (Nitto Denko Co., Tokyo) for
his support. Our thanks are due to Dr. Y. Hirose (Amano
Enzyme Co.) for supplying lipase. We are grateful to
Miss Tomoko Nomura for her help in the early phase of
this work.
References
1) Hill, A. S., Kovalev, B. G., Nikolaeva, L. N., and
Roelofs, W. L., Sex pheromone of the fall webworm
moth, Hyphantria cunea. J. Chem. Ecol., 8, 383–396
(1982).
´
2) Toth, M., Buser, H. R., Pen˜a, A., Arn, H., Mori, K.,
Takeuchi, T., Nicolaeva, L. N., and Kovalev, B. G.,
Identification of (3Z,6Z)-1,3,6-9,10-epoxyheneicosa-
triene and (3Z,6Z)-1,3,6-9,10-epoxyeicosatriene in the
sex pheromone of Hyphantria cunea. Tetrahedron Lett.,
30, 3405–3408 (1989).
3) Senda, S., Saika, T., and Furumori, K., Pheromone
control of fall webworm, Hyphantria cunea Drury
(Lepidoptera:Arctiidae). Nitto Giho, 31, 97–102 (1993).
4) Mori, K., and Ebata, T., Synthesis of optically active
pheromones with an epoxy ring, (+)-disparlure and both
the enantiomers of (3Z,6Z)-cis-9,10-epoxy-3,6-henico-
sadiene. Tetrahedron, 42, 3471–3478 (1986).
14) Millar, J. G., and Underhill, E. W., Short synthesis of
1,3Z,6Z,9Z-triene hydrocarbons. Lepidopteran sex at-
tractants. Can. J. Chem., 64, 2427–2430 (1986).
´
15) Soulie, J., Ta, C., and Lallemand, J.-Y., Access to
unsaturated chiral epoxides. I: Bisallylic chiral epoxide.
Application to the synthesis of Lepidopteran phero-
mones. Tetrahedron, 48, 443–452 (1992).
5) Mori, K., and Takeuchi, T., Synthesis of the enantiomers
of (3Z,6Z)-cis-9,10-epoxy-1,3,6-henicosatriene and