ꢁꢂꢈꢆ
ꢇꢆD
T. Shimizu et al.
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HRMS (FAB) calcd for C21H33O3 (M+H+): 333.2430, found:
333.2425.
1H NMR (270 MHz, CDCl3): d = 0.84 (d, E 2 6.9 Hz, 3H), 0.94 (d,
E 2 7.3 Hz, 3H), 0.96 (d, E 2 6.3 Hz, 3H), 4.56 (s, 2H), 4.66 (ddd,
E 2 10.9, 10.9, 4.6 Hz, 1H).
ꢁꢃG
Colorless solid.
13C NMR (67.8 MHz, CDCl3): d = 15.6, 20.8, 21.8, 23.0, 25.6, 31.7,
33.6, 42.0, 47.6, 54.2, 86.5.
1H NMR (270 MHz, CDCl3): d = 0.77 (s, 3H), 1.43 (s, 3H), 1.74 (br
s, 3H), 1.81 (br s, 3H), 3.65 (s, 3H), 4.83 (br s, 1H), 4.89 (br s, 1H),
5.47 (br s, 1H).
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1H NMR (270 MHz, CDCl3): d = 0.93 (d, E 2 6.3, 3H), 1.26 (s,
3H),1.43 (s, 3H), 3.92 (d, E 2 12.4 Hz, 1H), 3.99 (d, E 2 12.4 Hz,
1H), 4.82 (ddd, E = 10.7, 10.7, 4.4 Hz, 1H), 7.53 (m, 5H).
ꢁꢃH
Colorless solid.
1H NMR (270 MHz, CDCl3): d = 0.83 (s, 3H), 1.22 (s, 3H), 1.27 (s,
3H), 1.31 (s, 3H), 1.75 (br s, 3H), 2.62 (d, E = 14.5 Hz, 1H), 2.74 (d,
E = 14.2 Hz, 1H), 3.66 (s, 3H), 5.49 (br s, 1H).
13C NMR (67.8 MHz, CDCl3): d = 21.6, 24.8, 26.7, 27.7, 31.6, 34.0,
42.8, 50.6, 54.2, 54.8, 85.1, 125.4, 127.1, 128.0, 150.1.
ꢇꢃD
13C NMR (67.8 MHz, CDCl3): d = 16.9, 20.2, 26.6, 26.9, 27.2, 29.7,
30.6, 30.8, 32.9, 38.3, 40.9, 47.7, 48.5, 49.6, 51.4, 73.2, 81.4, 89.8,
127.6, 135.8, 171.8.
1H NMR (270 MHz, CDCl3): d = 1.05 (s, 9H), 3.05 (ddd, E 2 8.5,
5.4, 5.4 Hz, 1H), 3.57 (m, 2H), 3.78 (dd, E 2 10.6, 5.4 Hz, 1H), 4.08
(dd, E 2 10.6, 8.5 Hz, 1H), 4.41 (d, E 2 12.3 Hz, 1H), 4.49 (d,
E 2 12.3 Hz, 1H), 5.52 (m, 1H), 7.1–7.8 (m, 20H).
ꢁꢃI
Colorless solid.
13C NMR (67.8 MHz, CDCl3): d = 19.2, 26.8 (3C), 49.4, 54.1, 63.8,
70.6, 73.3, 83.5.
1H NMR (270 MHz, CDCl3): d = 0.82 (s, 3H), 0.94 (s, 3H), 0.98 (br
s, 3H), 1.34 (s, 3H), 1.79 (br s, 1H), 3.66 (s, 3H), 5.36 (dd, E = 10.5,
3.0 Hz, 1H), 5.53 (br s, 1H), 5.57 (br s, 1H).
ꢅꢌD
1H NMR (500 MHz, CDCl3): d = 0.12 (s, 9H), 1.20 (s, 3H), 1.60 (m,
1H), 1.70 (m, 1H), 1.91 (ddd, E = 14.6, 7.7, 7.7 Hz, 1H), 2.04 (m,
1H), 3.51 (m, 2H), 3.59 (m, 1H), 3.72 (br d, E = 8.6 Hz, 1H), 3.77
(m, 1H), 4.36 (d, E = 10.7 Hz, 1H), 4.48–4.55 (m, 4H), 4.60 (d,
E = 10.7 Hz, 1H), 7.25–7.35 (m,10H).
ꢆꢂD
Colorless solid.
1H NMR (270 MHz, CDCl3): d = 0.69 (s, 3H), 1.03 (s, 9H), 1.10 (s,
3H), 1.54 (br s, 3H), 1.61 (br s, 3H), 1.73 (br s, 3H), 3.65–3.85 (m,
2H), 5.48 (br s, 1H).
13C NMR (67.8 MHz, CDCl3): d = 14.7, 15.5, 19.1, 19.3, 21.0, 26.8
(3C), 27.0, 27.1, 28.3, 29.3, 29.5, 38.7, 39.0, 39.4, 46.1, 61.6, 82.3,
89.1, 124.9, 125.8, 127.2, 127.6 (4C), 129.5 (2C), 133.9, 134.0,
135.6 (4C), 136.2.
IR (CHCl3): n = 2965, 1706, 1428, 1112 cm-1.
HRMS (FAB) calcd for C36H51O2Si (M+H+): 543.3658, found:
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To a solution of the crude monochlateꢀ(0.1–1.0 mmol) in dioxane
(0.1–2.0 mL) was added Zn(OAc)2 (4.0 equiv.), and the mixture
was heated at 90 °C. After cooling, the mixture was filtrated
through a Celite pad and washed with CHCl3. After removal of the
solvents, the residue was purified by flash column chromatography
(hexane:EtOAc = 10:1–1:2). In the case of the alkenes ꢆꢉD and ꢆꢉE,
they were purified by HPLC (hexane:EtOAc = 2:1).
543.3638.
ꢆꢂE
Colorless solid.
1H NMR (270 MHz, CDCl3): d = 0.80 (s, 3H), 0.93 (s, 3H), 0.96 (s,
3H), 1.03 (s, 9H), 1.15 (s, 3H), 1.73 (br s, 3H), 3.71–3.78 (m, 2H),
5.34 (dd, E = 10.1, 2.7 Hz, 1H), 5.48 (d, E = 5.0 Hz, 1H), 5.54 (ddd,
E = 10.2, 6.0, 2.0 Hz, 1H).
ꢁꢃD
Colorless solid.
1H NMR (270 MHz, CDCl3): d = 0.67 (s, 3H), 1.11 (d, E = 7.2, 3H),
1.38 (s, 3H), 1.79 (br s, 3H), 3.67 (s, 3H), 4.51 (dd, E = 2.0, 1.7 Hz,
1H), 4.83 (dd, E = 2.0, 1.7 Hz, 1H), 5.48 (br s, 1H).
13C NMR (67.8 MHz, CDCl3): d = 15.0, 19.4, 21.2, 26.0, 26.6, 27.8,
28.6, 29.0, 35.2, 38.3, 38.5, 42.5, 47.8, 51.3, 81.7, 89.8, 106.8,
125.4, 134.7, 154.9, 171.7.
IR (CHCl3): n = 3023, 2963, 2930, 1724 cm-1.
MS (FAB): / = 355 (M+Na+).
IR (CHCl3): n = 2965, 1670 cm-1.
ꢆꢅDꢀ
Colorless solid.
1H NMR (270 MHz, CDCl3): d = 1.11 (s, 3H), 1.62 (br s, 3H), 5.75
(br s, 1H).
IR (CHCl3): n = 2950, 1671 cm-1.
HRMS (FAB) calcd for C19H27O (M+H+): 271.2062 found:
271.2059.
ꢁꢃE
Colorless solid.
1H NMR (270 MHz, CDCl3): d = 0.73 (s, 3H), 1.31 (s, 3H), 1.61 (br
s, 3H), 1.67 (d, E = 1.6 Hz, 3H), 1.77 (br, s, 3H), 3.67 (s, 3H), 5.52
(br s, 1H).
13C NMR (67.8 MHz, CDCl3): d = 16.6, 20.2, 20.2, 22.7, 26.8, 29.1,
29.4, 30.2, 31.7, 38.2, 43.5, 47.7, 48.9, 51.4, 81.4, 88.8, 123.2,
126.8, 135.6, 135.9, 170.8.
ꢆꢅE
Colorless solid.
1H NMR (270 MHz, CDCl3): d = 0.98 (d, E = 6.9 Hz, 3H), 1.17 (s,
3H), 5.75 (br s, 1H).
ꢆꢅF
Colorless solid.
ꢁꢃF
1H NMR (270 MHz, CDCl3): d = 1.02 (d, E = 6.9 Hz, 3H), 1.22 (s,
3H), 5.33 (br s, 1H), 5.75 (br s, 1H).
Colorless solid.
1H NMR (270 MHz, CDCl3): d = 0.93 (s, 3H), 1.04 (d, E = 7.2 Hz,
3H), 1.37 (s, 3H), 1.74 (br s, 3H), 1.82 (br s, 3H), 3.64 (s, 3H), 5.52
(br s, 1H).
IR (CHCl3): n = 2976, 1732 cm-1.
ꢆꢉD
Colorless solid.
1H NMR (400 MHz, CDCl3): d = 0.95 (s, 3H), 0.99 (d, E = 6.9, 3H),
1.27 (d, E = 6.6 Hz, 3H), 3.01 (m, 1H), 3.67 (s, 3H).
Synthesis 1999, No. 8, 1373–1385 ISSN 0039-7881 © Thieme Stuttgart · New York