Female Sex Pheromones of the Satin Moth, Leucoma salicis
FULL PAPER
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78.57, H 9.74. Its IR, H NMR and 13C NMR spectra were ident-
13C NMR (100 MHz, CHCl3): δ ϭ 14.1, 19.2, 22.7, 26.5, 26.7, 26.9,
27.8, 29.3, 29.48, 29.54, 29.6, 31.9, 54.0, 54.1, 56.1, 56.6, 61.9,
127.8, 129.8, 132.95, 133.18, 135.52, 135.57 ppm. C33H50O3Si
(522.8): calcd. C 75.81, H 9.64; found C 75.86, H 9.72.
ical with those of (2S,3R)-6.
(2S,3R,5Z)-1-(tert-Butyldiphenylsilyloxy)-cis-2,3-epoxy-5-hepta-
decene [(2S,3R)-7]: A solution of (2S,3R)-6 (10.6 g, 21.0 mmol) in
cyclohexane (20 mL) was added to an ice-cooled suspension of
Lindlar catalyst (5% Pd-CaCO3ϪPb2ϩ; 100 mg) in cyclohexane
(100 mL) under H2. After stirring for 3 h at room temperature, the
mixture was filtered through Celite, and the filtrate was concen-
trated under reduced pressure. The residue was purified by chroma-
tography (hexane/EtOAc, 100:1) to give (2S,3R)-7 (10.4 g, 98%) as
a colorless oil, n2D2 ϭ 1.5165. [α]2D2 ϭ Ϫ7.87 (c ϭ 1.03, CHCl3). IR
(film): ν˜max ϭ 2925 (s, CϪH), 2855 (s, CϪH), 1590 (w, CϭC), 1430
(m, SiϪC), 1110 (m, SiϪO). 1H NMR (400 MHz, CDCl3): δ ϭ
0.88 (t, J ϭ 6.9 Hz, 3 H, 17-H), 1.06 (s, 9 H, tBu), 1.23Ϫ1.35 (m,
18 H, 8, 9,10,11,12,13,14,15,16-H), 1.94 (dt, J ϭ 7.3, 7.3 Hz, 2 H,
7-H), 2.06 (ddd, J ϭ 15.1, 7.6, 6.6 Hz, 1 H, 4-Ha), 2.25 (ddd, J ϭ
15.1, 7.6, 6.6 Hz, 1 H, 4-Hb), 2.96 (ddd, J ϭ 6.6, 6.6, 4.2 Hz, 1 H,
3-H), 3.17 (ddd, J ϭ 5.9, 5.1, 4.2 Hz, 1 H, 2-H), 3.78 (dd, J ϭ 11.6,
5.1 Hz, 1 H, 1-Ha), 3.81 (dd, J ϭ 11.6, 5.9 Hz, 1 H, 1-Hb), 5.37
(dtt, J ϭ 10.8, 7.6, 1.4 Hz, 1 H, 5-H), 5.48 (dtt, J ϭ 10.8, 7.3,
1.4 Hz, 1 H, 6-H), 7.40 (m, 6 H, Ar-H), 7.69 (m, 4 H, Ar-H) ppm.
13C NMR (100 MHz, CHCl3): δ ϭ 14.1, 19.2, 22.7, 26.3, 26.8, 27.4,
29.27, 29.35, 29.5, 29.62, 29.64, 29.66, 31.9, 56.1, 56.7, 62.2, 123.6,
127.7, 129.8, 132.8, 133.2, 135.56, 135.62 ppm. C33H50O2Si (506.8):
calcd. C 78.20, H 9.94; found C 78.18, H 9.75.
(2S,3R,5R,6S)-8: n2D3 ϭ 1.5165. [α]2D3 ϭ ϩ7.4 (c ϭ 1.2, CHCl3). IR
(film): ν˜max ϭ 2925 (s, CϪH), 2855 (s, CϪH), 1590 (w, CϭC), 1430
(m, SiϪC), 1110 (m, SiϪO). 1H NMR (400 MHz, CDCl3): δ ϭ
0.88 (t, J ϭ 6.7 Hz, 3 H, 17-H), 1.06 (s, 9 H, tBu), 1.20Ϫ1.35 (m,
18 H, 8,9,10,11,12,13,14,15,16-H), 1.41 (m, 2 H, 7-H), 1.54 (ddd,
J ϭ 15.4, 7.5, 5.4 Hz, 1 H, 4-Ha), 1.61 (ddd, Jϭ 15.4, 7.1, 4.6 Hz,
1 H, 4-Hb), 2.93 (m, 2 H, 6-H), 3.06 (dt, J ϭ 7.1, 5.4 Hz, 1 H, 5-
H), 3.14 (dt, J ϭ 7.5, 4.6 Hz, 1 H, 3-H), 3.23 (dt, J ϭ 5.4, 4.6 Hz,
1 H, 2-H), 3.76 (dd, J ϭ 12.4, 5.4 Hz, 1 H, 1-Ha), 3.79 (dd, J ϭ
12.4, 5.4 Hz, 1 H, 1-Hb) ppm. 13C NMR (100 MHz, CHCl3): δ ϭ
14.1, 19.2, 22.7, 26.5, 26.7, 27.3, 27.8, 29.3, 29.48, 29.55, 29.63,
31.9, 53.9, 54.2, 56.5, 57.0, 62.2, 127.7, 129.78, 129.80, 133.06,
133.22, 135.54, 135.59 ppm. C33H50O3Si (522.8): calcd. C 75.81, H
9.64; found C 75.94, H 9.92.
(2R,3S,5R,6S)-1-(tert-Butyldiphenylsilyloxy)-cis-2,3-cis-5,6-diep-
oxyheptadecane [(2R,3S,5R,6S)-8]: In the same manner as that de-
scribed for the preparation of (2S,3R,5S,6R)-8, (2R,3S)-7 (3.67 g,
7.20 mmol) gave (2R,3S,5R,6S)-8 (721 mg, 19%) and its dia-
stereoisomer (2R,3S,5S,6R)-8 (1.81 g, 48%) as colorless oils.
(2R,3S,5R,6S)-8: n2D2 ϭ 1.5165. [α]2D4 ϭ ϩ0.53 (c ϭ 1.1, CHCl3).
C33H50O3Si (522.8): calcd. C 75.81, H 9.64; found C 75.54, H 9.76.
Its IR, H NMR and 13C NMR spectra were identical with those
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(2R,3S,5Z)-1-(tert-Butyldiphenylsilyloxy)-cis-2,3-epoxy-5-hepta-
decene [(2R,3S)-7]: In the same manner as that described for the
preparation of (2S,3R)-7, (2R,3S)-6 (4.00 g, 7.94 mmol) gave
of (2S,3R,5S,6R)-8. (2R,3S,5S,6R)-8: n2D3 ϭ 1.5161. [α]2D3 ϭ Ϫ7.2
(c ϭ 1.0, CHCl3). C33H50O3Si (522.8): calcd. C 75.69, H 9.77;
found C 75.54, H 9.76. Its IR, 1H NMR and 13C NMR spectra
were identical with those of (2S,3R,5R,6S)-8.
(2R,3S)-6 (3.80 g, 95%) as a colorless oil, n2D2 ϭ 1.5164. [α]2D2
ϭ
ϩ7.60 (c ϭ 1.14, CHCl3). C33H50O2Si (506.8): calcd. C 78.20, H
9.94; found C 78.26, H 10.23. Its IR, 1H NMR and 13C NMR
spectra were identical with those of (2S,3R)-7.
(2S,3R,5S,6R)-cis-2,3-cis-5,6-Diepoxy-1-heptadecanol [(2S,3R,5S,
6R)-9]: TBAF (1.0 in THF; 2.5 mL, 2.5 mmol) was added to a
solution of (2S,3R,5S,6R)-8 (1.26 g, 2.41 mmol) in THF (5 mL) at
room temperature. After stirring for 1 h at room temperature, the
reaction mixture was diluted with water, and extracted with Et2O.
The extract was washed with water and brine, dried over MgSO4,
and concentrated under reduced pressure. The residue was purified
by chromatography (hexane/EtOAc, 5:1) to give crude
(2S,3R,5S,6R)-9 (664 mg) as a colorless solid. The solid was recrys-
tallized from hexane/EtOAc to yield (2S,3R,5S,6R)-9 (559 mg,
81%) as colorless plates, m.p. 57.5Ϫ58.5 °C. [α]2D4 ϭ Ϫ5.35 (c ϭ
1.05, CHCl3). IR (KBr): ν˜max ϭ 3410 (s, OϪH), 2915 (s, CϪH),
2845 (s, CϪH). 1H NMR (400 MHz, CDCl3): δ ϭ 0.87 (t, J ϭ
6.8 Hz, 3 H, 17-H), 1.21Ϫ1.45 (m, 18 H, 8,9,10,11,12,13,14,15,16-
H), 1.52 (m, 2 H, 7-H), 1.86 (dd, J ϭ 7.1, 6.1 Hz, 2 H, 4-H), 1.92
(dd, J ϭ 6.8, 5.6 Hz, 1 H, OH), 2.96 (ddd, J ϭ 6.6, 6.1, 4.1 Hz, 1
H, 6-H), 3.08 (ddd, J ϭ 6.3, 6.1, 4.3 Hz, 1 H, 5-H), 3.20 (m, 2 H,
2,3-H), 3.77 (ddd, J ϭ 11.5, 5.6, 1.5 Hz, 1 H, 1-Ha), 3.87 (ddd, J ϭ
11.5, 6.8, 4.4 Hz, 1 H, 1-Hb) ppm. 13C NMR (100 MHz, CHCl3):
δ ϭ 14.1, 22.7, 26.6, 27.0, 27.8, 29.3, 29.48, 29.52, 29.6, 31.9, 54.1,
54.4, 56.1, 56.8, 60.4, 60.6 ppm. C17H32O3 (284.4): calcd. C 71.79,
H 11.34; found C 71.85, H 11.14.
(2S,3R,5S,6R)-1-(tert-Butyldiphenylsilyloxy)-cis-2,3-cis-5,6-diep-
oxyheptadecane [(2S,3R,5S,6R)-8]: A solution of MCPBA (70% pu-
rity, 3.58 g, 14.5 mmol) in CH2Cl2 (30 mL) was added dropwise to
a solution of (2S,3R)-7 (6.18 g, 12.3 mmol) in CH2Cl2 (50 mL) at
0 °C. The mixture was stirred for 5 h at room temperature, then
quenched with saturated aqueous NaHCO3, and extracted with
Et2O. The extract was washed with water, saturated aqueous
Na2SO3 and brine, dried over MgSO4, and concentrated under re-
duced pressure. The residue was purified by chromatography (hex-
ane/EtOAc, 30:1) to give a diastereomixture (6.26 g). The dia-
stereomeric ratio was determined by HPLC analysis: The mixture
of (2S,3R,5S,6R)-8 and (2S,3R,5R,6S)-8 was analyzed by HPLC
(Pegasil-Senshu column, 25 cm ϫ 4.6 mm; eluent: hexane/EtOAc,
20:1; flow rate: 1.0 mL/min), tR of (2S,3R,5S,6R)-8: 13.7 min
(40%), tR of (2S,3R,5R,6S)-8: 17.4 (60%) min. The diastereomix-
ture (6.26 g) was repeatedly separated by MPLC (column 50 cm ϫ
7 cm, silica gel SIL-5020Ϫ12B 50
Ϯ 20 µm, hexane/Et2O,
40:1Ϫ20:1) using ca. 2 g at a time to yield (2S,3R,5S,6R)-8 (less
polar) (1.50 g, 23%) and its diastereoisomer (2S,3R,5R,6S)-8 (more
polar) (3.69 g, 57%) as colorless oils.
(2S,3R,5S,6R)-8: n2D3 ϭ 1.5161. [α]2D3 ϭ Ϫ0.58 (c ϭ 1.2, CHCl3). IR
(film): ν˜max ϭ 2925 (s, CϪH), 2855 (s, CϪH), 1590 (w, CϭC), 1430
(m, SiϪC), 1110 (m, SiϪO). 1H NMR (400 MHz, CDCl3): δ ϭ
0.86 (t, J ϭ 6.8 Hz, 3 H, 17-H), 1.04 (s, 9 H, tBu), 1.20Ϫ1.50 (m, 20
H, 7,8,9,10,11,12,13,14,15,16-H), 1.61 (ddd, J ϭ 14.6, 5.9, 5.9 Hz, 1
H, 4-Ha), 1.64 (ddd, J ϭ 14.6, 6.1, 6.1 Hz, 1 H, 4-Hb), 2.89 (m, 1
H, 6-H), 2.99 (ddd, J ϭ 7.0, 5.6, 4.4 Hz, 1 H, 5-H), 3.10 (ddd, J ϭ
6.2, 6.1, 4.1 Hz, 1 H, 3-H), 3.18 (ddd, J ϭ 5.6, 5.4, 4.1 Hz, 1 H, 2-
(2R,3S,5R,6S)-cis-2,3-cis-5,6-Diepoxy-1-heptadecanol [(2R,3S,5R,
6S)-9]: In the same manner as that described for the preparation
of (2S,3R,5S,6R)-9, (2R,3S)-8 (718 mg, 1.37 mmol) gave
(2R,3S,5R,6S)-9 (277 mg, 70%) as colorless plates, m.p. 57.5Ϫ58.5
°C. [α]2D4 ϭ ϩ5.52 (c ϭ 1.07, CHCl3). C17H32O3 (284.4): calcd. C
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71.79, H 11.34; found C 71.82, H 11.53. Its IR, H NMR and 13C
NMR spectra were identical with those of (2S,3R,5S,6R)-9.
H), 3.71 (dd, J ϭ 11.5, 5.6 Hz, 1 H, 1-Ha), 3.84 (dd, J ϭ 11.5, (2S,3R,5R,6S)-cis-2,3-cis-5,6-Diepoxy-1-heptadecanol [(2S,3R,5R,
5.4 Hz, 1 H, 1-Hb), 7.39 (m, 6 H, Ar-H), 7.66 (m, 4 H, Ar-H) ppm. 6S)-9]: In the same manner as that described for the preparation
Eur. J. Org. Chem. 2003, 1300Ϫ1307
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