T. Oishi et al. / Tetrahedron Letters 44 (2003) 7315–7319
7319
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1.52–1.59 (2H, m, H4ax, H11ax), 2.32 (1H, dt, J=12.0, 4.5
Hz, H11eq), 2.41 (1H, dt, J=12.0, 4.5 Hz, H4eq), 2.52
(1H, dt, J=11.5, 4.5 Hz, H14eq), 2.96 (1H, ddd, J=11.5,
9.5, 4.5 Hz, H13), 3.03 (1H, ddd, J=11.5, 9.5, 4.5 Hz,
H12), 3.24 (1H, ddd, J=10.5, 10.0, 5.0 Hz, H4), 3.29–
3.34 (2H, m, H5, H10), 3.40 (1H, ddd, J=9.5, 5.0, 1.5
Hz, H2), 3.50 (1H, ddd, J=11.5, 9.5, 4.5 Hz, H15), 3.63
(1H, dd, J=10.5, 5.0 Hz, H17), 3.73 (1H, dd, J=10.5, 1.5
Hz, H17), 3.74 (1H, ddd, J=11.5, 10.0, 4.5 Hz, H3), 3.78
(1H, t, J=10.5 Hz, H1ax), 3.81 (1H, d, J=9.0 Hz, H6 or
H9), 3.86 (1H, d, J=9.5 Hz, H6 or H9), 4.12 (1H, dd,
J=10.5, 5.0 Hz, H1eq), 4.37 (1H, d, J=11.5 Hz), 4.53
(1H, d, J=12.0 Hz), 4.55 (1H, d, J=11.5 Hz), 4.59 (1H,
d, J=12.0 Hz), 5.58 (1H, d, J=15.0 Hz), 5.61 (1H, d,
J=15.0 Hz), 7.17–7.32 (10H, m, Ph); ESI MS calcd for
C39H54O8SiNa (M+Na+) 701, found 701; 2b: 1H NMR
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t
t
(500 MHz, CDCl3) l 0.95 (9H, s, Bu), 1.02 (9H, s, Bu),
1.44 (1H, td, J=11.5, 11.0 Hz, H15ax), 1.53–1.61 (2H, m,
H4ax, H12ax), 2.27 (1H, dt, J=11.5, 4.5 Hz, H12eq), 2.32
(1H, ddd, J=14.0, 6.5, 2.0 Hz, H9), 2.43 (1H, dt, J=
12.0, 4.5 Hz, H4eq), 2.50 (1H, dt, J=11.0, 4.5 Hz, H15eq),
2.67 (1H, ddd, J=14.0, 9.5, 4.5 Hz, H9), 2.90–2.98 (2H,
m, H13, H14), 3.22 (1H, ddd, J=10.5, 10.0, 5.5 Hz, H2),
3.26 (1H, ddd, J=11.5, 9.5, 4.5 Hz, H5), 3.33 (1H, ddd,
J=9.5, 4.5, 2.0 Hz, H2), 3.36 (1H, ddd, J=10.0, 5.0, 2.0
Hz, H17), 3.44 (1H, ddd, J=11.5, 9.5, 4.5 Hz, H11), 3.48
(1H, ddd, J=11.5, 10.0, 4.5 Hz, H16), 3.62 (1H, dd,
J=10.0, 5.0 Hz, H18), 3.72 (1H, dd, J=10.0, 2.0 Hz,
H18), 3.75 (1H, ddd, J=11.5, 10.0, 4.5 Hz, H3), 3.78
(1H, t, J=10.5 Hz, H1ax), 3.93 (1H, ddd, J=9.5, 5.0, 2.0
Hz, H6), 4.12 (1H, dd, J=10.5, 5.5 Hz, H1eq), 4.35 (1H,
d, J=11.5 Hz), 4.52 (1H, d, J=12.5 Hz), 4.53 (1H, d,
J=11.5 Hz), 4.59 (1H, d, J=12.5 Hz), 5.63 (1H, dd,
J=11.5, 5.0 Hz, H7), 5.68 (1H, dddd, J=11.5, 9.5, 6.5,
2.0 Hz, H8), 7.16–7.31 (10H, m, Ph); ESI MS calcd for
C40H56O8SiNa (M+Na+) 715, found 715.
10. (a) Fukuzawa, S.-I.; Tsuchimoto, T.; Hotaka, T.;
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Angew. Chem., Int. Ed. 1998, 37, 965–969.
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16. Sterochemistry of the tetracyclic ethers was determined
by 1H NMR analysis and NOE experiments. 2a: 1H
t
17. Aramini, A.; Brinchi, L.; Germani, R.; Savelli, G. Eur. J.
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NMR (500 MHz, CDCl3) l 0.95 (9H, s, Bu), 1.01 (9H, s,
tBu), 1.43 (1H, ddd, J=11.5, 11.5, 11.5 Hz, H14ax),