J.S. Yadav et al. / Tetrahedron 65 (2009) 3536–3544
3541
C27H45NO2S (447.72): C 72.43, H 10.13, N 3.13, S 7.16; found: C 72.42,
H 10.10, N 3.10, S 7.13%.
4.14. (R)-1-(1-Isocyano-3-methyl-dodecane-1-sulfonyl)-4-
methyl-benzene 22
4.10. (10R,14R)-10,14-Dimethyloctadec-1-ene 1
Compound 22 (0.11 g, 80%) was prepared from 21 (0.11 g,
0.38 mmol), tosylmethyl isocyanide (TosMIC, 0.11 g, 0.57 mmol),
tetrabutylammonium iodide (0.042 g, 0.11 mmol), 40% aqueous
NaOH (8.72 mL), and dichloromethane (8.72 mL) following the
same procedure as described for the synthesis of 16. Compound 22
To liq. NH3 (50 mL) at ꢂ33 ꢁC, was added lithium (0.01 g,
1.63 mmol), followed by dialkylated TosMIC 17 (0.075 g, 0.16 mmol)
in ether (5 mL), ethanol (0.12 mL). After 2 h, ammonia was allowed
to evaporate by bringing the reaction mixture to room temperature.
Then water was added and extracted with ether. The organic layer
was washed with water, dried (Na2SO4), concentrated, and purifi-
cation by column chromatography afforded pheromone 1 (0.03 g,
80%) as a colorless oil. Rf¼compound is eluted in pentane;
was colorless liquid. Rf¼0.2 (SiO2, 20% Et2O in pentane); IR (neat):
n
2133, 1600 cmꢂ1 1H NMR (200 MHz, CDCl3):
;
d
7.84 (d, 2H,
J¼8.08 Hz), 7.40 (d, 2H, J¼8.08 Hz), 4.33 (dd, 1H, J¼3.67, 3.67 Hz),
2.51 (s, 3H), 2.08–1.98 (m, 2H), 1.72–1.15 (m, 20H), 0.87 (t, 3H,
J¼6.61 Hz); 13C NMR (75 MHz, CDCl3):
d 11.3, 14.1, 18.6, 20.3, 21.7,
25
25
[
n
a
]
ꢂ1.72 (c 1.3, CHCl3); [lit.2 [
a
]
ꢂ1.70 (c 1.27, CHCl3)] IR (neat):
22.5, 26.6, 27.4, 29.0, 32.4, 72.7, 120.2, 130.0, 138.0, 146.5, 164.7;
MASS (EIMS): m/z 363 [M]þ. Elemental analysis calcd for
C21H35NO2S (365.24): C 69.99, H 9.65, N 3.83, S 8.77; found: C 69.92,
H 9.61, N 3.81, S 8.75%.
D
D
2925, 1638 cmꢂ1 1H NMR (500 MHz, CDCl3):
; d 5.82 (ddt, 1H,
J¼6.37, 10.35, 17.52 Hz), 4.90–4.99 (m, 2H), 2.04 (m, 2H), 1.03–1.43
(m, 26H), 0.89 (t, 3H, J¼6.37 Hz), 0.843 (d, 3H, J¼6.37 Hz), 0.840 (d,
3H, J¼6.37 Hz). 13C NMR (75 MHz, CDCl3):
d 138.9, 114.2, 37.4, 36.8,
33.8, 32.7, 32.7, 30.0, 29.5, 29.3, 29.2, 29.0, 27.1, 24.5, 23.0, 19.7, 14.2;
MASS: 279 [MꢂH]þ. Elemental analysis calcd for C20H40 (280.53): C
85.63, H 14.37; found: C 85.02, H 13.92%.
4.15. 1-((5R,9R)-7-Isocyano-5,9-dimethyl-octadecane-7-
sulfonyl)-4-methyl-benzene 23
Compound 23 (0.10 g, 90%) was prepared from 22 (0.09 g,
0.25 mmol) in DMSO/ether (1:5, 6 mL), prewashed sodium hydride
(0.018 g, 0.75 mmol) in ether (5 mL), 1-iodo-2-methyl-hexane 11
(0.05 g, 0.25 mmol) in ether (5 mL) following the same procedure
as described for the synthesis of 17. Compound 23 was pale yellow
4.11. 4-Benzyl-3-(R-2-methyl-1-oxo undecyl)-1,3-oxazolidine-
2-thione 18
Compound 18 (2.71 g, 95%) was prepared from 7 (1.89 g,
7.61 mmol) using LDA (14.50 mmol, generated from 9.06 mL of
1.6 M n-BuLi in hexane and 2.06 mL diisopropylamine), lithium
chloride (1.84 g, 43.52 mmol), bromononane (7.51 g, 36.2 mmol)
following the same procedure as described for the synthesis of 8.
oily liquid. Rf¼0.1 (SiO2, 20% EtOAc in pentane); IR (neat):
n 2130,
7.85 (d, 2H, J¼8.30 Hz),
1600 cmꢂ1 1H NMR (300 MHz, CDCl3):
;
d
7.40 (d, 2H, J¼8.30 Hz), 2.5 (s, 3H), 2.06–1.86 (m, 4H), 1.64–1.04 (m,
30H), 0.88 (t, 6H, J¼6.79 Hz); 13C NMR (75 MHz, CDCl3):
d 164.7,
Compound 18 was a pale yellow oil. Rf¼0.7 (SiO2, 30% EtOAc in
146.2, 138.1, 131.2, 129.7, 125.4, 120.2, 119.1, 80.0, 46.2, 37.1, 32.6,
31.8, 31.3, 30.3, 29.7, 29.1, 23.4, 22.6, 21.7, 14.0, 11.3; MASS (EIMS):
m/z 451 [M]þ. Elemental analysis calcd for C27H47NO2S (449.73): C
72.11, H 10.53, N 3.11, S 7.13; found: C 72.08, H 10.51, N 3.09, S 7.12%.
25
hexane); [
a]
ꢂ4.43 (c 1.05, CHCl3); IR (neat):
n 3027, 2925, 2854,
D
1605, 1454, 1148 cmꢂ1 1H NMR (300 MHz, CDCl3):
; d 7.27–7.14 (m,
5H), 4.39–4.29 (m, 1H), 4.23–4.17 (m, 1H), 4.02–3.97 (m, 1H), 3.09
(dd, 1H, J¼5.28, 5.28 Hz), 3.04–2.89 (m, 2H), 2.64–2.56 (m, 2H),
1.74–1.65 (m, 2H), 1.42–1.28 (m, 15H), 0.88 (t, 3H, J¼5.28 Hz); 13C
4.16. (5R,9R)-5,9-Dimethyloctadecane 2
NMR (75 MHz, CDCl3): d 165.5, 137.7, 129.1, 128.3, 126.3, 72.93, 67.6,
41.7, 31.8, 29.5, 29.4, 29.3, 29.1, 28.7, 22.6, 14.1; MASS (ESI-MS): m/z
376 [MþH]þ. Elemental analysis calcd for C22H33NO2S (375.57): C
70.36, H 8.86, N 3.73, S 8.54; found: C 70.34, H 8.56, N 3.70, S 8.52%.
Compound 2 (0.03 g, 80%) was prepared from dialkylated Tos-
MIC 23 (0.06 g, 0.14 mmol) using lithium (0.01 g, 1.48 mmol), in
ether (5 mL), ethanol (0.12 mL) following the same procedure as
described for the synthesis of 1. Compound 2 was colorless oil.
25
4.12. (R)-2-Methyl-undecan-1-ol 20
Rf¼compound is eluted in pentane; [
a]
ꢂ1.88 (c 0.965, Hexane)
D
[lit.3 [
a
]
25 c ꢂ1.88 (c 2.56, hexane)]; IR (neat):
n
2925 cmꢂ1; 1H NMR
D
Compound 20 (0.64 g, 65%) was prepared from 18 (2 g,
5.32 mmol) using DIBAL-H (10 mL) (20 wt % solution in toluene)
and NaBH4 (0.14 g, 3.83 mmol) following the same procedure as
(500 MHz, CDCl3): d 1.03–1.43 (m, 30H), 0.88–0.89 (t, 6H,
J¼6.37 Hz), 0.843 (d, 3H, J¼6.37 Hz), 0.840 (d, 3H, J¼6.37 Hz); 13C
NMR (75 MHz, CDCl3):
d 37.4, 37.2, 36.8, 32.75, 32.74, 32.72, 31.9,
described for the synthesis of 10. Compound 20 was colorless oil.
30.0, 29.7, 29.6, 29.3, 29.3, 27.1, 24.5, 22.7, 19.7, 14.2, 14.1. MASS: 283
[MþH]þ. Elemental analysis calcd for C20H42 (282.55): C 85.02, H
14.98; found: C 84.68, H 14.59%.
25
Rf¼0.3 (SiO2, 20% EtOAc in hexane); [
(neat):
(300 MHz, CDCl3):
0.85 (m, 6H); 13C NMR (75 MHz, CDCl3):
a
]
þ4.8 (c 0.34, CHCl3). IR
D
n
3395, 2972, 2928, 1379, 1315, 1163 cmꢂ1
;
1H NMR
d
3.52–3.32 (m, 2H), 1.75–1.03 (m, 17H), 0.92–
d
68.3, 35.7, 33.1, 31.8, 29.9,
4.17. 4-Benzyl-3-(R-2-methyl-1-oxo decyl)-1,3-oxazolidine-2-
thione 24
29.5, 29.2, 26.9, 22.6, 16.5, 14.0; MASS (ESI-MS): m/z 226 [Mþ39]þ.
Elemental analysis calcd for C12H26O (186.33): C 77.35, H 14.06;
found: C 77.32, H 14.03%.
Compound 24 (2.61 g, 95%) was prepared from 7 (1.89 g,
7.61 mmol) using LDA (14.49 mmol, generated from 9.06 mL of
1.6 M n-BuLi in hexane and 2.06 mL diisopropylamine), lithium
chloride (1.84 g, 43.52 mmol), bromooctane (7.0 g, 36.2 mmol)
following the same procedure as described for the synthesis of 8.
4.13. (R)-1-Iodo-2-methyl-undecane 21
Compound 21 (0.16 g, 95%) was prepared from 20 (0.10 g,
0.54 mmol) using TPP (0.31 g, 1.18 mmol), imidazole (0.08 g,
1.18 mmol), and iodine (0.22 g, 0.88 mmol) following the same
procedure as described for the synthesis of 11. Compound 21 was
Compound 24 was a pale yellow oil. Rf¼0.7 (SiO2, 30% EtOAc in
25
hexane); [
a
]
D
ꢂ4.01 (c 1.08, CHCl3); IR (neat):
n 3027, 2925, 2854,
1605, 1454, 1147 cmꢂ1 1H NMR (300 MHz, CDCl3):
; d 7.28–7.14 (m,
colorless liquid. Rf¼0.2 (SiO2, 20% EtOAc in hexane); IR (neat):
n
5H), 4.39–4.29 (m, 1H), 4.21 (t, 1H, J¼8.30 Hz), 4.01 (t, 1H,
J¼6.79 Hz), 3.10 (dd, 1H, J¼5.28, 4.53 Hz), 2.97 (ddd, 2H, J¼3.02,
3.02, 3.02 Hz), 2.64–2.56 (m, 1H), 1.74–1.65 (m, 2H), 1.47–1.16 (m,
2928, 2856, 760 cmꢂ1; 1H NMR (200 MHz, CDCl3):
d 3.25–3.09 (m,
2H), 1.55–1.08 (m, 17H), 0.99 (d, 3H, J¼5.87 Hz), 0.90 (m, 3H); 13C
NMR (75 MHz, CDCl3):
d
36.4, 34.7, 31.8, 29.6, 29.5, 29.2, 26.8, 22.6,
14H), 0.89 (t, 3H, J¼6.79 Hz); 13C NMR (75 MHz, CDCl3):
d 165.9,
20.5, 17.8, 14.0; MASS (ESI-MS): m/z 295 [Mꢂ1]þ.
137.8, 129.2, 128.4, 126.4, 73.0, 67.7, 41.6, 31.9, 31.7, 29.4, 29.1, 29.0,