Z. Wang et al. / Tetrahedron 62 (2006) 6967–6972
6971
Compound 5a: colorless liquid, isolated yield 53%
122.34, 122.76, 122.85, 123.33, 125.98, 126.46, 126.94,
133.43, 138.17, 139.51, 139.80, 142.18, 145.04, 145.32,
145.40, 145.61, 149.11, 149.50, 150.41, 150.98. HRMS
calcd for C17H24S: 260.1599; found: 260.1604.
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(120 mg). H NMR (CDCl3): d 1.08 (d, J¼3.6 Hz, 3H),
2.00 (s, 3H), 2.06 (s, 3H), 2.14 (s, 3H), 3.28 (q,
J¼11.4 Hz, 1H), 3.96 (s, CH3, 3H), 7.04 (d, J¼4.5 Hz,
2H), 7.31 (d, J¼4.5 Hz, 2H). 13C NMR (CDCl3): d 11.07,
11.84, 12.57, 14.87, 50.13, 55.18, 113.59, 129.46, 130.40,
134.91, 135.89, 139.95, 142.35, 157.51. HRMS calcd for
C16H20O: 228.1514; found: 228.1513.
Compound 6a: quenched with saturated NaHCO3. Colorless
liquid, isolated yield 95%, GC yield 99%. 1H NMR (CDCl3,
TMS): d 0.72–0.98 (m, 14H), 1.31–1.43 (m, 8H), 2.03–2.10
(m, 6H), 5.19 (t, J¼7.2 Hz, 1H), 5.78 (s, 1H), 7.21–7.39 (m,
5H). 13C NMR (CDCl3, TMS): d 13.91, 14.22, 14.65, 14.84,
21.54, 21.82, 23.11, 24.41, 29.91, 30.02, 32.15, 32.57, 73.85,
126.06, 126.48, 127.90, 129.22, 135.74, 139.04, 143.47.
HRMS calcd for C23H36O: 328.2766; found: 328.2757.
Compound 5b: colorless liquid, isolated yield 75%
(192 mg), two isomers in 3:1. H NMR (CDCl3) of the
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main product: d 0.54–0.88 (m, 12H), 1.19–2.35 (m, 8H),
3.05–3.30 (m, 1H), 6.77–7.14 (m, 5H). 13C NMR (CDCl3)
of the main product: d 6.81, 15.21, 15.44, 15.55, 18.53,
19.46, 19.66, 20.74, 52.45, 125.47, 128.09, 128.37,
137.61, 140.63, 141.98, 144.24, 145.04. HRMS calcd for
C19H26: 254.2034; found: 254.2037.
Compound 5f: colorless liquid as a mixture of two double
bond positional isomers (5:2) in 99% combined GC yield
(combined isolated yield 86%). The NMR data of 5f were
consistent with those reported.17
Compound 5c: brown liquid, 3:1 mixture of positional dou-
ble bond isomers, combined isolated yield 71% (175 mg).
1H NMR (CDCl3) of the mixture: d 0.37 (t, J¼7.5 Hz,
3H), 0.85–1.19 (m, 10H), 1.61–2.67 (m, 10H), 3.43 (t,
J¼4.4 Hz, 1H), 5.46 (q, J¼11.1 Hz, 1H), 6.19 (d,
J¼1.8 Hz, 1H), 3.10 (d, J¼1.6 Hz, 0.3H), 6.40–6.46 (m,
1.3H), 7.37 (d, J¼0.9 Hz, 1H), 7.42 (d, J¼0.9 Hz, 0.3H).
13C NMR (CDCl3) of the mixture: d 6.68, 11.23, 11.25,
13.30, 14.30, 14.59, 15.14, 15.36, 18.32, 18.74, 19.59,
20.01, 22.01, 27.62, 27.86, 46.06, 50.54, 51.15, 104.74,
107.58, 110.93, 111.02, 113.16, 129.68, 132.14, 140.21,
140.38, 141.29, 142.00, 145.36, 145.49, 150.89, 152.89,
153.23. HRMS calcd for C17H24O: 244.1827; found:
244.1822.
Compound 6b: colorless liquid, isolated yield 65%, GC
yield 82%. 1H NMR (CDCl3, TMS): d 0.85–0.97 (m,
17H), 1.25–1.59 (m, 10H), 1.93–2.11 (m, 8H), 4.57 (t,
J¼4.8 Hz, 1H), 4.96 (t, J¼7.2 Hz, 1H). 13C NMR (CDCl3,
TMS): d 13.97, 14.18, 14.23, 14.60, 15.00, 19.69, 21.57
(2CH2), 23.18, 24.79, 29.18, 29.89, 31.97, 32.46, 37.87,
72.71, 128.73, 136.77, 139.05, 141.78. HRMS calcd for
C20H38O: 294.2923; found: 294.2929.
Compound 5g: colorless liquid as a mixture of two double
bond positional isomers (4:3) in 85% combined GC yield
(combined isolated yield 70%). The NMR data of 5g were
consistent with those reported.17
Compound 5d: colorless liquid, three isomers in 1:1:1, iso-
lated yield 86% (284 mg). 1H NMR (CDCl3) of the mixture:
d 0.30 (t, J¼7.2 Hz, 3H), 0.81–1.19 (m, 27H), 1.25–1.78 (m,
14H, including 1.43 (d, J¼3.6 Hz, 3H) and 1.70 (d,
J¼3.6 Hz, 3H)), 2.00–2.60 (m, 14H), 3.37 (s, 1H), 3.14
(t, J¼4.2 Hz, 1H), 3.52 (s, 1H), 5.29–5.43 (m, 2H), 6.95
(d, J¼4.2 Hz, 2H), 7.01(d, J¼4.2 Hz, 2H), 7.11(d, J¼4.2 Hz,
2H), 7.34 (d, J¼4.2 Hz, 2H), 7.46 (d, J¼4.2 Hz, 2H). 13C
NMR (CDCl3) of the mixture: d 6.76, 10.85, 10.90, 12.79,
12.90, 13.81, 14.17, 14.26, 15.02, 15.18, 15.36, 15.48,
17.79, 17.83, 18.49, 18.68, 19.44, 19.56, 19.66, 19.94,
20.37, 20.68, 26.31, 28.08, 49.81, 50.40, 52.46, 56.08,
56.82, 111.04, 111.77, 118.96, 119.27, 119.50, 128.64,
128.99, 129.90, 131.25, 131.38, 131.41, 136.50, 139.22,
139.39, 140.11, 142.08, 145.05, 145.22, 145.36, 145.53,
146.14, 146.46, 149.77. HRMS calcd for C19H25Br:
332.1140; found: 332.1134.
Compound 5h: colorless liquid, isolated yield 81%
(321 mg). H NMR (CDCl3): d 0.65–0.70 (m, 5H), 0.86–
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1.04 (m, 9H), 1.17–1.60 (m, 14H), 1.99–2.59 (m, 8H),
3.23–3.47 (br, 1H), 3.81 (s, 3H), 6.88 (d, J¼4.2 Hz, 2H),
7.14 (d, J¼4.2 Hz, 2H). 13C NMR (CDCl3): d 13.92,
14.00, 14.07, 22.94, 23.07 (2CH2), 23.09, 24.82, 25.46,
26.30, 27.89, 32.68, 33.06, 33.20, 52.52, 55.14, 113.50,
129.45, 130.58, 140.59, 141.08, 141.57, 143.56, 157.52.
HRMS calcd for C28H44O: 396.3392; found: 396.3386.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China, the Major State Basic Research
Development Program (G2000077502-D), and Dow
Corning Corporation. Cheung Kong Scholars Program,
Qiu Shi Science and Technologies Foundation, and BASF
are gratefully acknowledged.
Compound 5e: colorless liquid, three isomers in 2:1:1, iso-
lated yield 78% (203 mg). 1H NMR (CDCl3) of the mixture:
d 0.35 (t, J¼7.2 Hz, 3H), 0.97–1.32 (m, 27H), 1.59 (d,
J¼3.6 Hz, 3H), 1.71(d, J¼3.6 Hz, 3H), 1.76–2.02 (m, 6H),
2.12–2.71 (m, 14H), 3.39 (t, J¼4.2 Hz, 1H), 3.74 (s,
0.5H), 3.90 (s, 0.5H), 5.36 (q, J¼7.2 Hz, 1H), 6.73 (d,
J¼2.7 Hz, 1H), 6.78 (d, J¼2.7 Hz, 1H), 6.80–6.95 (m,
3H), 7.02–7.08 (m, 3H), 7.18 (d, J¼2.7 Hz, 2H). 13C NMR
(CDCl3) of the mixture: d 6.62, 10.84, 11.09, 12.76, 12.82,
13.60, 13.66, 14.17, 14.28, 14.43, 15.16, 15.41, 17.81,
18.44, 19.67, 19.88, 20.00, 20.29, 21.91, 26.16, 27.90,
45.54, 51.06, 51.30, 53.04, 57.20, 111.43, 112.19, 122.25,
References and notes
1. Chen, J.; Song, Q.; Wang, C.; Xi, Z. J. Am. Chem. Soc. 2002,
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2. (a) Song, Q.; Chen, J.; Jin, X.; Xi, Z. J. Am. Chem. Soc. 2001,
123, 10419–10420; (b) Song, Q.; Li, Z.; Chen, J.; Wang, C.; Xi,
Z. Org. Lett. 2002, 4, 4627–4629.