Synthesis of the Pheromone of the Painted Apple Moth
1563
-
4-Hb), 3.73 (3H, s, OMe), 3.76 (1H, seemingly quint,
7.8 Hz, CHO). NMR dC (100 MHz, CDCl3): 4.51,
14.1, 18.1, 22.7, 25.3, 25.8, 29.3, 29.56, 29.63, 31.9,
37.3, 40.4, 71.0, 134.7, 155.6, 194.0. Anal. Found:
=
=
J
5.8 Hz, 5-H), 5.83 (1H, dt,
J
15.6, 1.2 Hz,
=
J
2-H), 6.97 (1H, dt,
15.6, 3.5 Hz, 3-H). NMR dC
-
-
(100 MHz, CDCl3): 4.56, 4.53, 14.1, 18.1, 22.7,
25.3, 25.8, 29.3, 29.57, 29.59, 29.7, 31.9, 37.2, 40.2,
51.4, 71.3, 122.7, 146.5, 166.9. Anal. Found: C,
C, 71.37; H, 12.21
71.12; H, 11.94
z. Calcd. for C21H42O2Si: C,
z
.
68.44; H, 11.71
H, 11.53
z
. Calcd. for C22H44O3Si: C, 68.69;
(E)-1,1-Dibromo-5-tert-butyldimethylsilyloxy-2-
pentadecene (14). To a stirred solution of 13 (1.18 g,
3.30 mmol) and carbon tetrabromide (1.64 g,
4.94 mmol) in CH2Cl2 (10 ml) was added portionwise
z
.
(E)-5-tert-Butyldimethylsilyloxy-2-pentadecen-1-ol
(
12). To a stirred solution of 11 (1.42 g, 3.70 mmol)
triphenylphosphine (2.60 g, 9.91 mmol) at 0
9C. Af-
in dry toluene (10 ml), DIBAL-H (1.01
M
in toluene;
ter stirring for 15 min at 0 C, the mixture was diluted
9
-
8.0 ml, 8.0 mmol) was added dropwise at
78
9
C
with hexane, ˆltered through Celite, and concentrat-
ed under reduced pressure. The residue was puriˆed
-
under argon. After stirring for 1 h at 78
9C, the
mixture was quenched with saturated aqueous
Rochelle's salt and then Et2O was added. The result-
ing slurry was stirred at room temperature until two
clear layers became apparent. These layers were
separated, and the aqueous layer was extracted with
Et2O. The combined organic layer was successively
washed with water and brine, dried over MgSO4, and
concentrated under reduced pressure. The residue
by chromatography (hexane:AcOEt 200:1) to give
=
14 (1.48 g, 88
z
) as a colorless oil, n2D4 1.4955, IR nmax
(ˆlm) cm-1: 1255 (m, Si–C), 1095 (m, Si–O). NMR
dH (400 MHz, CDCl3): 0.03 and 0.04 (6H, each s,
=
7.0 Hz,
Me), 0.88 (9H, s, tert-Bu), 0.88 (3H, t,
J
16-H), 1.20–1.38 (16H, m, 8, 9, 10, 11, 12, 13, 14,
=
15-H), 1.40 (2H, m, 7-H), 2.21 (1H, ddd,
J
14.3,
=
J
7.6, 5.8 Hz, 5-Ha), 2.27 (1H, ddd,
14.3, 7.6, 5.8
=
=
5.8 Hz,
was puriˆed by chromatography (hexane:AcOEt
Hz, 5-Hb), 3.70 (1H, seemingly quint,
J
) as a colorless oil, n2D3
6-H), 5.92 (1H, dt,
dd,
2-H). NMR dC (100 MHz, CDCl3):
J
15.5, 7.6 Hz, 4-H), 6.09 (1H,
=
20:1) to give 12 (1.27 g, 96
z
1.4535, IR nmax (ˆlm) cm-1: 3320 (s, O–H), 1255 (m,
Si–C), 1095 (m, Si–O). NMR dH (400 MHz, CDCl3):
J
=
15.5, 10.1 Hz, 3-H), 6.91 (1H, d,
J
=
10.1 Hz,
-
-
4.4,
4.5,
0.04 (6H, s, Me), 0.88 (9H, s, tert-Bu), 0.88 (3H, t,
J
14.1, 18.1, 22.7, 25.3, 25.9, 29.3, 29.6, 29.7, 31.9,
37.1, 40.8, 71.6, 129.0, 135.9, 137.0. This oil was em-
ployed for the next step without further puriˆcation.
=
7.0 Hz, 15-H), 1.20–1.45 (19H, m, 6, 7, 8, 9, 10,
=
14.1,
11, 12, 13, 14-H and OH), 2.16 (1H, ddd,
J
6.5, 5.8 Hz, 4-Ha), 2.23 (1H, ddd, J 14.1, 6.5, 5.8
=
=
Hz, 4-Hb), 3.66 (1H, seemingly quint,
J
5.8 Hz,
5.1, 5.1 Hz, 1-H), 5.67 (1H,
15.6, 5.1 Hz, 2-H), 5.68 (1H, dt, 15.6, 6.5
Hz, 3-H). NMR dC (100 MHz, CDCl3):
4.39, 14.1, 18.1, 22.7, 25.4, 25.9, 29.3, 29.60,
29.63, 29.8, 31.9, 36.9, 40.2, 63.8, 72.0, 129.8, 131.7.
Anal. Found: C, 70.68; H, 12.50 . Calcd. for
C21H44O2Si: C, 70.72; H, 12.43
(E)-1-Bromo-5-tert-butyldimethylsilyloxy-2-pen-
tadecene (15). To a stirred solution of Pd(OAc)2
(5.3 mg, 0.024 mmol) and PPh3 (28 mg, 0.11 mmol)
in benzene (2 ml) was added a solution of 14 (100 mg,
0.196 mmol) at room temperature under argon. To
=
J
5-H), 4.10 (2H, dd,
dt,
J
=
J
=
-
4.51,
-
this mixture, (n-Bu)3SnH (0.06 ml, 0.22 mmol) was
z
added at room temperature, and the resulting mix-
ture was stirred for 1 h at room temperature. The
mixture was diluted with hexane, successively washed
with water and brine, dried over MgSO4, and concen-
trated under reduced pressure. The residue was puri-
z
.
(E)-5-tert-Butyldimethylsilyloxy-2-pentadecenal
13). To stirred solution of 12 (214 mg,
(
a
=
0.601 mmol) in CH2Cl2 (10 ml) was added MnO2
(2.50 g, 28.8 mmol) at room temperature. After stir-
ring for 4 h at room temperature, the mixture was
diluted with Et2O, ˆltered through Celite, and con-
centrated under reduced pressure. The residue was
ˆed by chromatography (hexane:AcOEt 200:1) to
give 15 (85 mg, quant.) as a colorless oil, n2D4 1.4790,
IR nmax (ˆlm) cm-1: 1255 (m, Si–C), 1085 (m, Si–O).
NMR
dH (300 MHz, CDCl3): 0.03 and 0.04 (6H, each
=
s, Me), 0.88 (9H, s, tert-Bu), 0.88 (3H, t,
J
7.0 Hz,
=
puriˆed by chromatography (hexane:AcOEt 100:1)
16-H), 1.20–1.44 (16H, m, 8, 9, 10, 11, 12, 13, 14,
to give 13 (203 mg, 95
z
) as a colorless oil, n2D3 1.4535,
15-H), 2.27 (1H, dd,
J
=
7.5, 5.7 Hz, 5-H), 3.69 (1H,
IR nmax (ˆlm) cm- : 2725 (w, C–H), 1700 (s, C O),
seemingly quint,
J
5.7 Hz, 6-H), 5.91 (1H, dt,
J
1
=
=
=
=
=
1640 (w, C C), 1255 (m, Si–C), 1095 (m, Si–O).
NMR H (400 MHz, CDCl3): 0.04 and 0.06 (6H, each
s, Me), 0.87 (3H, t,
15.3, 7.5 Hz, 4-H), 6.04 (1H, d,
J
7.2 Hz, 1-H),
=
15.3, 10.2 Hz, 3-H), 6.60 (1H, m,
d
6.38 (1H, dd,
J
=
-
-
J
7.1 Hz, 15-H), 0.88 (9H, s,
2-H). NMR dC (100 MHz, CDCl3): 4.51, 4.41,
14.1, 18.1, 22.7, 25.4, 25.9, 29.3, 29.6, 29.7, 31.9,
37.1, 40.9, 71.9, 105.8, 127.9, 132.7, 136.0. HRMS
tert-Bu), 1.20–1.38 (16H, m, 7, 8, 9, 10, 11, 12, 13,
=
14-H), 1.45 (2H, m, 6-H), 2.44 (1H, dddd,
J
14.3,
=
7.3, 5.8, 1.2 Hz, 4-Ha), 2.51 (1H, dddd,
J
14.3, 7.3,
(EI) m z (M+–H): calcd. for C H OBrSi, 429.2188;
W
22
42
=
5.8, 1.2 Hz, 4-Hb), 3.83 (1H, seemingly quint,
J
5.8
15.6, 7.8, 1.2 Hz, 2-H),
15.6, 7.3 Hz, 3-H), 9.51 (1H, d,
found, 429.2184.
=
J
Hz, 5-H), 6.13 (1H, ddt,
6.89 (1H, dt,
J
=
J
=