J.-H. Liu et al. / Tetrahedron 66 (2010) 1267–1273
1273
129.7, 131.2, 135.7. MS (ESI, m/z): 661.5 (MþNaþ), 678.4 (MþKþ).
HRMS calcd for C35H62O4S2SiNa [MþNaþ] 661.3757, found
661.3710.
0.94 (s, 9H), 0.97 (d, J¼6.9 Hz, 6H), 1.20–1.60 (m, 37H), 2.20–2.40
(m, 5H), 3.40 (m, 2H), 3.60 (m, 2H), 3.72 (m, 1H), 3.80 (s, 3H), 3.80–
4.00 (m, 4H), 4.06 (m, 2H), 4.50 (m, 2H), 4.84 (t, J¼4.8 Hz, 1H), 5.20
(m, 1H), 5.89 (m, 1H), 6.86 (d, J¼8.4 Hz, 2H), 7.26 (m, 2H); 13C NMR
4.1.20. 1-{2-[14-(tert-Butyl-dimethyl-silanyloxy)-7-(7S)-(4-me-
thoxy-benzyloxy)-8-(8S)-propenyloxy-tetradecyl]-[1,3]dithian-2-yl}-
3-[5-(5R)-(5-[1,3]dioxolan-2-yl-pentyl)-2,2-dimethyl-[1,3]dioxolan-
4-(4R)-yl]-propan-2-ol (26). To a solution of dithioacetal 6 (338 mg,
0.53 mmol) in THF (2 mL) at ꢀ78 ꢁC under N2 atmosphere was
added HMPA (0.3 mL) and n-BuLi (0.36 mL, 0.58 mmol, 1.6 M in
hexane) successively. After stirring at same temperature for 1 h, the
epoxide 5 (159 mg, 0.53 mmol) in THF (1 mL) was added rapidly.
The mixture was allowed to warm to rt and stand overnight. The
reaction was quenched with water at 0 ꢁC and the water layer was
extracted with ether (ꢂ3). The combined organic layers were
washed with brine, dried over Na2SO4, evaporated in vacuo. The
residue was purified with gel column chromatography (EtOAc/pe-
troleum ether, 1:3) to give 210 mg (40%) of 26 as colorless oil. 1H
(CDCl3, 75 MHz)
d
ꢀ5.0, 14.3, 15.5, 18.6, 22.4, 22.7, 22.8, 22.9, 24.1,
24.3, 25.9, 26.0, 26.1, 26.2, 27.0, 27.4, 27.5, 28.5, 29.0, 29.4, 29.7, 29.8,
29.9, 32.0, 32.1, 32.7, 32.8, 33.0, 33.8, 34.0, 35.6, 35.8, 37.7, 37.9, 38.7,
40.2, 44.1, 55.5, 63.4, 65.1, 72.0, 76.1, 79.5, 80.6, 82.0, 82.8, 104.8,
107.5, 108.7, 113.9, 129.7, 131.1, 132.7, 142.2, 200.5. MS (ESI, m/z):
1045.7 (MþNaþ), 1046.7 (MþNaþþHþ). HRMS calcd for
C50H86O10SiNa [MþNaþ] 897.5888, found 897.5873.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (No. 20372068 and 30672528) and
Science and Technology Commission of Shanghai Municipality
(07QH14018 and 08JC1422200).
NMR (CDCl3, 300 MHz) d, 0.06 (s, 6H), 0.95 (s, 9H), 1.20–1.80 (m,
41H), 1.80–2.06 (m, 6H), 2.20–2.40 (m, 1H), 2.70–3.10 (m, 4H), 3.36
(m, 1H), 3.56 (m, 4H), 3.70 (m, 2H), 3.80 (s, 3H), 3.80–4.00 (m, 4H),
4.18 (m, 1H), 4.40–4.60 (m, 2H), 4.80 (t, J¼4.8 Hz, 1H), 5.96 (m, 1H),
6.85 (d, J¼8.4 Hz, 2H), 7.25 (d, J¼8.4 Hz, 2H); 13C NMR (CDCl3,
Supplementary data
1H NMR spectra for compound 2, 5, 6, 9, 11–15, 18, 20–24, and
26–27. 13C NMR spectra for compound 2, 5, 6, 11–13, 15, 22, 24, and
26. Supplementary data associated with this article can be found in
75 MHz)
d
ꢀ5.0, 9.6, 18.6, 22.9, 24.1, 24.2, 25.3, 26.0, 26.2, 26.6, 27.4,
27.5, 27.6, 29.7, 29.8, 29.9, 30.3, 30.5, 32.1, 32.6, 32.7, 33.0, 34.0, 39.8,
40.0, 40.8, 41.2, 42.3, 44.9, 45.3, 52.5, 52.6, 55.5, 63.5, 65.0, 65.8,
66.2, 67.6, 72.8, 76.8, 79.6, 80.6, 81.3, 81.5, 83.8, 99.9, 104.8, 108.3,
108.6, 113.9, 129.0, 129.8, 131.2, 146.6, 158.9, 159.4. MS (ESI, m/z):
References and notes
961.7 (MþNaþ), 962.6 (MþNaþþHþ). HRMS calcd for C51H90O9S2
-
SiNa [MþNaþ] 961.5693, found 961.5643.
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obtained as colorless oil. 1H NMR (CDCl3, 300 MHz)
d 0.05 (s, 6H),