504
B. Zhou, Y. Li / Tetrahedron Letters 53 (2012) 502–504
0.88 (s, 9H), 0.87 (s, 9H), 0.06 (s, 6H), 0.03 (s, 6H); 13C NMR (100 MHz, CDCl3) d
168.9, 78.6, 70.0, 60.8, 53.8, 48.2, 32.7, 25.7, 25.7, 25.7, 25.7, 25.7, 25.7, 18.1,
17.9, -4.7, -4.8, -5.5, -5.6; IR
max: 2955, 2858, 1471, 1255, 1114 cmꢁ1; LRMS
Acknowledgments
m
(EI, 70 eV) m/z (%) 370 (M+-CH3, 4), 73 (100); HRMS (EI) calcd for C18H36NSi2O3
This work was supported by National Science & Technology Ma-
jor Project ‘Key New Drug Creation and Manufacturing Program’,
China (Number: 2009ZX09102-026).
(M+): 370.2234, found 370.2216. Compound 12: ½a 2D5
ꢀ
+96.6 (c 0.355, CHCl3); 1
H
NMR (CDCl3, 300 MHz) d 4.50 (t, J = 9.0 Hz, 1H), 4.41 (q, J = 8.1 Hz, 1H), 3.81
(dd, J = 12.3, 7.8 Hz, 1H), 3.73 (dd, J = 10.2, 3.6 Hz, 1H), 3.61 (dd, J = 10.2, 6.0 Hz,
1H), 3.49 (q, J = 11.4 Hz, 1H), 2.89 (dd, J = 17.7, 9.0 Hz, 1H), 2.35 (dd, J = 17.7,
6.6 Hz, 1H), 1.94–1.84 (m, 1H), 0.88 (s, 18H), 0.06 (s, 6H), 0.04 (s, 6H); 13C NMR
(100 MHz, CDCl3) d 166.8, 75.7, 73.8, 61.6, 54.6, 54.4, 32.0, 25.8, 25.8, 25.8,
Supplementary data
25.6, 25.6, 25.6, 18.2, 17.8, -4.5, -5.0, -5.4, -5.5; IR
1114 cmꢁ1; LRMS (EI, 70 eV) m/z (%) 385 (M+, 3), 73 (100); HRMS (EI) calcd for
19H39NSi2O3 (M+): 385.2469, found 385.2474.
mmax: 2954, 2857, 1471, 1255,
Supplementary data associated with this article can be found, in
C
12. Curran, D. P. J. Am. Chem. Soc. 1982, 104, 4024.
13. Compound 3: ½a D25
ꢀ
+29.5 (c 0.8, CHCl3); 1H NMR (CDCl3, 300 MHz) d 6.11 (d,
References and notes
J = 2.1 Hz, 1H), 5.40 (d, J = 2.1 Hz, 1H), 4.34 (dt, J = 6.0, 4.2 Hz, 1H), 3.71 (dq,
J = 5.7, 10.2 Hz, 2H), 2.83 (br s, 1H), 2.64 (dd, J = 18.0, 6.3 Hz, 1H), 2.32 (dd,
J = 18.0, 4.5 Hz, 1H), 0.86 (s, 18H), 0.07 (s, 3H), 0.05 (s, 3H), 0.04 (s, 3H), 0.03 (s,
3H); 13C NMR (100 MHz, CDCl3) d 204.6, 145.0, 118.9, 69.1, 63.4, 53.6, 47.2,
1. Regev, A.; Schiff, E. R. Adv. Inter. Med. 2001, 46, 107.
2. Innaimo, S. F.; Sieffer, M.; Bisacchi, G. S.; Standring, N.; Zahler, R.; Colonno, R. J.
Antimicrob. Agents Chemother. 1997, 41, 1444.
3. De Man, R. A.; Wolters, L. M. M.; Nevens, F.; Chua, D.; Sherman, M.; Lai, C. L.;
Gadano, A.; Lee, Y.; Mazzotta, F.; Thomas, N.; DeHertogh, D. Hepatology 2001,
34, 578.
4. Lai, C.; Rosmawati, M.; Lao, J.; Vlierberghe, H.; Anderson, F.; Thomas, N.; De
Hertogh, D. J. Hepatology 2001, 34, 24.
5. Bisacchi, G. S.; Chao, S. T.; Bachand, C.; Daris, J. P.; Innaimo, S. F.; Jacobs, G. A.;
Kocy, O.; Lapointe, P.; Martel, A.; Merchant, Z.; Slusarchyk, W. A.; Sundeen, J. E.;
Young, M. G.; Colonno, R. J.; Zahler, R. Bioorg. Med. Chem. Lett. 1997, 7, 127.
6. (a) Bisacchi, G. S.; Chao, S. T.; Bachard, C.; Daris, J. P.; Innaimo, S.; Jacobs, G. A.;
Kocy, O.; Lapointe, P.; Martel, A.; Merchant, Z.; Slusarchyk, W. A.; Sundeen, J. E.;
Young, M. G.; Colonno, R.; Zahler, R. Bioorg. Med. Chem. Lett. 1997, 7, 127; (b)
Bisacchi, G. S.; Sundeen, J. E. W.O. Patent 9809964, 1998.; (c) Pendri, Y. R.; Chen,
C. P. H.; Patel, S. S. et al. U.S. Patent 0192912, 2004.; (d) Guo, L. W.; Xiao, Y. J.;
Yang, L. P. Chin. Chem. Lett. 2006, 17, 907; (e) Ziegler, F. E.; Sarpong, M. A.
Tetrahedron 2003, 59, 9013; (f) Zhou, M. X.; Reiff, E. A. et al. U.S. Patent
7786300, 2010.
25.8, 25.8, 25.8, 25.7, 25.7, 25.7, 18.2, 17.9, -4.6, -4.8, -5.4, -5.5; IR mmax: 3432,
2954, 2857, 1714, 1471, 1255, 1103 cmꢁ1; LRMS (EI, 70 eV) m/z (%) 355 (M+-
CH3, 4), 73 (100); HRMS (EI) calcd for C18H35Si2O3 (M+): 355.2125, found
355.2121.
14. Other reducing systems examined include NaBH4, L-selectride, KBH4, CeCl3-
NaBH4, LiAlH4, LiAlH(OtBu)3.
15. Compound 2: ½a D25
ꢀ
ꢁ37 (c 0.035, CHCl3); 1H NMR (CDCl3, 400 MHz) d 5.39 (s,
1H), 5.12 (s, 1H), 4.38–4.29 (m, 2H), 3.56 (dd, J = 10.0, 5.2 Hz, 1H), 3.29 (dd,
J = 10.0, 8.8 Hz, 1H), 2.96 (dd, J = 10.4 Hz, 1H), 2.78–2.73 (m, 1H), 1.97 (ddd,
J = 13.6, 5.6, 4.4 Hz, 1H), 1.83 (dq, J = 13.6, 2.4 Hz, 1H), 0.88 (s, 9H), 0.87 (s, 9H),
0.09 (s, 6H), 0.04 (s, 3H), 0.03 (s. 3H); 13C NMR (100 MHz, CDCl3) d 154.2, 117.7,
75.5, 75.4, 64.6, 54.8, 41.9, 25.8, 25.8, 25.8, 25.7, 25.7, 25.7, 18.2, 17.8, -4.8, -4.8,
-5.4, -5.5; IR m
max: 3324, 2956, 2856, 1471, 1257, 1122, 1078 cmꢁ1; LRMS (EI,
70 eV) m/z (%) 357 (M+-CH3, 3), 73 (100); HRMS (EI) calcd for C18H37Si2O3 (M+):
357.2281, found 357.2286.
16. Bonnal, C.; Chavis, C.; Lucas, M. J. Chem. Soc. Perkin Trans. 1 1994, 1401.
17. Compound 13: ½a D25
ꢀ
+31 (c 0.7, CHCl3); 1H NMR (CDCl3, 300 MHz) d 7.65 (s, 1H),
7.52–7.49 (m, 2H), 7.38–7.28 (m, 3H), 5.56 (s, 2H), 5.51 (m, 1H), 5.16 (s, 1H),
4.87 (s, 2H), 4.83 (s, 1H), 4.45–4.40 (m, 1H), 3.83–3.72 (m, 2H), 2.66 (br s, 1H),
2.32–2.13 (m, 2H), 0.92 (s, 9H), 0.89 (s, 9H), 0.09 (s, 6H), 0.08 (s, 3H), 0.07 (s,
3H); 13C NMR (100 MHz, CDCl3) d 161.0, 159.0, 154.3, 149.3, 138.7, 136.6,
128.3, 128.3, 128.3, 128.3, 127.9, 115.7, 111.1, 72.3, 67.9, 64.0, 55.9, 54.8, 40.4,
7. For reviews on the Swern oxidation, see: (a) Tidwell, T. T. Synthesis 1990, 857;
(b) Tidwell, T. T. Org. React. 1990, 39, 297.
8. Ireland, R. E.; Norbeck, D. W. J. Org. Chem. 1985, 50, 2198.
9. (a) Gao, Y.; Hanson, R. M.; Klunder, J. M.; Ko, S. Y.; Masamune, H.; Sharpless, K.
B. J. Am. Chem. Soc. 1987, 109, 5765; (b) Johnson, R. A.; Sharpless, K. B. In
Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH: New York, 1993; pp 103–
105.
26.0, 26.0, 26.0, 25.8, 25.8, 25.8, 18.4, 18.0, -4.5, -4.6, -5.3, -5.4; IR mmax: 3492,
3326, 2927, 2856, 1774, 1608, 1253 cmꢁ1; LRMS (EI, 70 eV) m/z (%) 595 (M+,
12), 450 (100); HRMS (EI) calcd for C31H49Si2O3N5 (M+): 595.3374, found
595.3368.
10. (a) Okamoto, S.; Kobayashi, Y.; Kato, H.; Hori, K.; Takahashi, T.; Tsuji, J.; Sato, F.
J. Org. Chem. 1988, 53, 5590; (b) Shing, T. K. M.; Wong, W. F.; Cheng, H. M.;
Kwok, W. S.; So, K. H. Org. Lett. 2007, 9, 753.
18. Compound 1: ½a D25
ꢀ
+26.0 (c 1.0, H2O); 1H NMR (DMSO-d6, 300 MHz) d 10.59 (s,
11. Compound 11: ½a D25
ꢀ
ꢁ32 (c 0.2, CHCl3); 1H NMR (CDCl3, 300 MHz) d 4.49–4.45
1H), 7.65 (s, 1H), 6.42 (s, 2H), 5.34 (t, J = 9.3 Hz, 1H), 5.08 (s, 1H), 4.88–4.82 (m,
2H), 4.53 (s, 1H), 4.21 (s, 1H), 3.51 (t, J = 5.7 Hz, 1H), 2.52–2.48 (m, 1H), 2.25–
2.15 (m, 1H), 2.05–1.98 (m, 1H); 13C NMR (100 MHz, DMSO-d6) d 157.3, 153.9,
151.9, 151.7, 136.5, 116.7, 109.7, 70.8, 63.5, 55.6, 54.5.
(m, 1H), 4.42 (dd, J = 9.9, 7.5 Hz, 1H), 4.11 (q, J = 9.9 Hz, 1H), 3.96 (dd,
J = 13.2,7.5 Hz, 1H), 3.58 (dd, J = 10.5, 6.9 Hz, 1H), 3.48 (dd, J = 10.5, 6.6 Hz, 1H),
2.77 (dd, J = 16.8, 6.0 Hz, 1H), 2.37 (dd, J = 16.8, 3.0 Hz, 1H), 2.28–2.19 (m, 1H),