(C-24), 16.07 (C-25), 16.38 (C-28), 16.85 (C-26), 16.91 (C-27),
18.73 (C-5), 18.73 (C-6), 18.73 (C-7), 21.33 (C-11), 22.03
(C-16), 23.69 (C-12), 25.23 (C-30), 27.69 (C-20), 27.90 (C-2),
28.77 (C-23), 33.95 (C-15), 37.31 (C-10), 38.99 (C-1), 39.08
(C-4), 41.92 (C-8), 42.20 (C-19), 42.26 (C-14), 44.98 (C-18),
46.78 (C-21), 49.82 (C-13), 50.66 (C-9), 55.05 (C-17), 78.54
(C-3), 110.7 (C-29), 148.4 (C-22). Assignments are exchange-
of C-2 and C-6 may be interchangeable. EIMS m/z 191 (100%),
204 (93), 396 (Mϩ, 55).
34a (oil) in C6D6. δH 0.96 (6H, s, Me-24 and Me-25), 0.99
(3H, d, J 6.4, Me-28), 1.03 (3H,s, Me-23), 1.03 (3H, s, Me-27),
1.05 (m, H-2), 1.06 (m, H-1), 1.09 (m, H-6), 1.17 (3H,s, Me-26),
1.23 (m, H-19), 1.28 (m, H-3), 1.38 (m, H-16), 1.48 (m, H-5),
1.51 (m, H-2), 1.52 (m, H-3), 1.55 (m, H-15), 1.57 (m, H-18),
1.61 (m, H-17), 1.62 (2H, m, H-11), 1.65 (m, H-15), 1.74 (m,
H-1), 1.78 (m, H-12), 1.86 (m, H-19), 1.92 (m, H-12), 2.03 (m,
H-16), 2.26 (m, H-6), 2.30 (m, H-20), 2.43 (m, H-9), 5.15 (bd, J
9.1, H-22), 5.23 (bdd, J 17, 1.8, H-22), 5.47 (dd, J 6.4, 3.1, H-7),
5.99 (m, H-21). δC 13.36 (C-25), 18.49 (C-11), 18.63 (C-28),
19.45 (C-2), 21.52 (C-23), 22.40 (C-27), 24.71 (C-6), 27.60 (C-
26), 28.76 (C-16), 31.47 (C-20), 33.15 (C-24), 33.30 (C-4), 34.22
(C-12), 34.66 (C-19), 35.40 (C-10), 35.85 (C-18), 39.31 (C-1),
42.69 (C-3), 43.82 (C-13), 49.45 (C-9), 51.66 (C-5), 51.71 (C-
15), 53.58 (C-17), 114.4 (C-22), 118.5 (C-7), 139.6 (C-21), 146.0
(C-8). EIMS m/z 367 (100%), 382 (Mϩ, 18)
34c (oil) in C6D6. δH 5.66 (m, H-22), 5.67 (m, H-21), 1.75 (3H,
bd, J 5.8, Me-29), 1.04 (3H, m, Me-28). δC 12.9 (C-29), 13.4 (C-
25), 18.5 (C-6), 18.7 (C-28), 19.4 (C-2), 21.5 (C-24), 22.4 (C-27),
24.6 (C-12), 24.7 (C-11), 27.6 (C-26), 28.8 (C-20), 36.0 (C-17),
33.1 (C-23), 33.3 (C-4), 34.3 (C-16), 34.4 (C-15), 35.2 (C-19),
35.4 (C-10), 39.3 (C-1), 42.7 (C-3), 43.8 (C-13), 49.5 (C-9), 51.7
(C-5), 51.7 (C-14), 53.7 (C-18), 118.5 (C-7), 123.7 (C-22), 131.4
(C-21), 146.0 (C-8). EIMS m/z 381 (100%), 382 (Mϩ, 16)
35 (oil) in C6D6. δH 0.89 (m, H-5), 0.92 (m, H-1), 0.989 (3H,s,
Me-24), 1.01 (3H, s, Me-25), 1.02 (3H, s, Me-23), 1.07 (3H, s,
Me-26), 1.11 (3H,s, Me-27), 1.22 (m, H-12), 1.25 (m, H-3), 1.38
(m, H-15), 1.39 (m, H-7), 1.45 (m, H-3), 1.48 (3H, m, H-2, H-6,
H-9), 1.62 (m, H-11), 1.63 (2H, m, H-2, H-6, H-15), 1.68 (m,
H-12), 1.70 (m, H-7), 1.75 (m, H-1), 1.78 (m, H-11), 1.87 (m,
H-16), 1.98 (m, H-16), 2.05 (m, H-13), 2.17 (m, H-19), 2.28
(m, H-19), 2.32 (2H, m, H-20), 2.65 (m, H-17), 5.11 (bs, H-28),
5.14 (bd, J 10.4, H-22), 5.18 (bs, H-28), 5.21 (bd, J 15.7, H-22),
5.98 (m, H-21). Assignments of H-11 and H-12 may be
exchangeable. δC 16.13 (C-26), 16.46 (C-25), 17.50 (C-27), 19.06
(C-2, C-6), 21.75 (C-24), 22.14 (C-12), 25.38 (C-11), 28.65
(C-16), 33.32 (C-20), 33.37 (C-15), 33.55 (C-4), 33.57 (C-23),
35.37 (C-7), 37.50 (C-10), 38.26 (C-19), 40.88 (C-1), 41.29
(C-8), 42.42 (C-3), 44.32 (C-17), 44.93 (C-13), 50.19 (C-14),
51.33 (C-9), 57.29 (C-5), 109.6 (C-28), 114.6 (C-22), 138.9
(C-21), 146.6 (C-18). Assignments of C-11 and C-12 or C-15
and C-20 are exchangeable. EIMS m/z 191 (100%), 205 (37), 299
(28), 341 (37), 396 (Mϩ, 36).
25
able between C-26 and C-27, and between C8 and C14. [α]D
(EtOH) ϩ6.63 (c = 0.090).
32a (oil) in C6D6. δH 0.90 (m, H-1), 0.93 (dd, J 12, 1.8, H-5),
0.97 (3H, s, Me-24), 0.99 (3H, s, Me-25), 1.48 (m, H-7), 1.03
(3H, s, Me-23), 1.09 (3H, s, Me-26), 1.11 (d, J 7.2, Me-28), 1.26
(m, H-3), 1.29 (3H, s, Me-27), 1.40 (m, H-12), 1.43 (m, H-15),
1.44 (2H, m, H-2, H-6), 1.48 (m, H-3), 1.52 (m, H-19), 1.58
(m, H-9), 1.62 (m, H-19), 1.65 (m, H-6), 1.66 (m, H-7), 1.67
(m, H-12), 1.70 (m, H-2), 1.77 (m, H-1), 2.03 (m, H-11), 2.09
(m, H-15), 2.12 (m, H-20), 2.22 (m, H-20), 2.59 (m, H-11), 2.68
(m, H-18), 5.15 (bd, J 10.4, H-22), 5.24 (dd, J 16.8, 1.6, H-22),
5.96 (m, H-21). δC 16.65 (C-25), 17.62 (C-26), 18.90 (C-2), 19.03
(C-6), 20.08 (C-28), 21.88 (C-24), 22.05 (C-12), 23.03 (C-27),
23.26 (C-11), 29.31 (C-16), 30.97 (C-15), 31.81 (C-18), 32.65 (C-
20), 33.48 (C-4), 33.66 (C-23), 34.95 (C-19), 35.79 (C-7), 37.96
(C-10), 40.81 (C-1), 41.46 (C-8), 42.29 (C-3), 52.07 (C-9), 56.90
(C-14), 57.26 (C-5), 114.5 (C-22), 134.7 (C-17), 139.4 (C-21),
1
139.8 (C-13). Assignments of H and 13C at C-2 and C-6 are
interchangeable. EIMS m/z 191 (100%), 205 (39), 299 (16), 382
(Mϩ, 61).
32c (oil) in C6D6. δC 12.95 (C-29), 16.64 (C-25), 17.62 (C-26),
18.91 (C-2), 19.04 (C-6), 20.13 (C-28), 21.89 (C-24), 22.11
(C-12), 23.10 (C-27), 23.33 (C-11), 29.42 (C-16), 30.17 (C-15),
31.02 (C-18), 32.21 (C-20), 33.49 (C-4), 33.66 (C-23), 35.68
(C-19), 35.79 (C-7), 37.9 8 (C-10), 40.84 (C-1), 41.53 (C-8),
42.31 (C-3), 52.12 (C-9), 56.90 (C-14), 57.26 (C-5), 123.8
(C-22), 131.2 (C-21), 134.9 (C-17), 139.7 (C-13). EIMS m/z 191
(100), 205 (38), 341 (37), 396 (Mϩ, 36).
33a (oil) in C6D6. δH 0.92 (2H, m, H-1, H-5), 1.00 (3H, s,
Me-24), 1.01 (d, J 6.9, Me-28), 1.02 (3H, s, Me-26), 1.04 (3H, s,
Me-23), 1.07 (3H, s, Me-25), 1.17 (3H, s, Me-27), 1.27 (m, H-3),
1.30 (m, H-15), 1.45 (m, H-19), 1.47 (m, H-3), 1.48 (2H, m, H-2,
H-6), 1.61 (2H, m, H-16, H-19), 1.65 (m, H-1), 1.68 (2H, m,
H-2, H-6), 1.70 (m, H-7), 1.78 (m, H-15), 1.82 (2H, m, H-9,
H-7), 1.93 (m, H-18), 1.94 (m, H-11), 2.15 (m, H-11), 2.17 (m,
H-20), 2.23 (m, H-20), 2.53 (m, H-17), 5.15 (bd, J 10.1, H-22),
5.21 (dd, J 17.0, 1.7, H-22), 5.39 (dd, J 3.5, 3.1, H-5), 5.97 (m,
H-21). δC 15.35 (C-28), 15.9 (C-25), 17.09 (C-26), 18.87 (C-2),
19.08 (C-6), 21.95 (C-24), 22.86 (C-27), 23.93 (C-11), 24.44
(C-16), 32.04 (C-15), 32.19 (C-20), 33.34 (C-4), 33.65 (C-23),
34.57 (C-18), 35.13 (C-7), 35.33 (C-19), 37.84 (C-10), 38.53
(C-8), 40.58 (C-1), 42.29 (C-3), 48.66 (C-9), 48.77 (C-17), 50.61
(C-14), 57.26 (C-5), 114.4 (C-22), 116.2 (C-12), 139.4 (C-21),
149.1 (C-13). Assignments of C-2 and C-6 are interchangeable.
EIMS m/z 190 (100%), 367 (13), 382 (Mϩ, 29)
36 in C6D6. δH 0.94 (dd, J 12, 1.7, H-5), 0.95 (m, H-1), 0.99
(3H, s, Me-24), 1.02 (3H, s, Me-25), 1.05 (3H, s, Me-23), 1.12
(3H, s, Me-26), 1.18 (3H, d, J 7.3, Me-28), 1.30 (m, H-2), 1.33
(m, H-16), 1.33 (3H, s, Me-27), 1.38 (m, H-15), 1.40 (m, H-19),
1.41 (2H, m, H-6, H-11), 1.52 (m, H-2), 1.55 (2H, m, H-7), 1.58
(m, H-21), 1.60 (m, H-11), 1.63 (2H, m, H-9, H-16), 1.65 (2H,
m, H-6, H-19), 1.74 (m, H-20), 1.80 (m, H-1), 1.84 (2H, m,
H-20, H-21), 1.86 (m, H-15), 2.08 (m, H-12), 2.10 (m, H-18),
2.65 (dd, J 14.5, 3.3, H-12), 2.86 (m, H-22). δC 16.47 (C-25),
17.96 (C-20, C-26), 19.03 (C-2, C-6), 20.71 (C-28), 21.84 (C-11),
21.90 (C-24), 22.48 (C-27), 25.11 (C-12), 26.38 (C-21), 27.44
(C-19), 29.20 (C-16), 30.33 (C-22), 31.12 (C-15), 33.39 (C-4),
33.67 (C-23), 34.70 (C-18), 34.97 (C-7), 37.87 (C-10), 40.60
(C-1), 41.50 (C-8), 42.31 (C-3), 44.63 (C-14), 51.00 (C-9), 56.76
(C-5), 133.83 (C-13), 136.52 (C-17). EIMS m/z 176 (100), 191
33b (oil) in C6D6. δH 5.61 (2H, m, H-21 and H-22), 1.76 (3H,
d, J 5.0, Me-29), 1.04 (3H, s, J 6.4, Me-28). δC 15.44 (C-28),
15.91 (C-25), 17.10 (C-26), 18.13 (C-29), 18.88 (C-2), 19.08
(C-6), 21.95 (C-24), 22.88 (C-27), 23.93 (C-11), 24.50 (C-16),
31.05 (C-20), 32.05 (C-15), 33.34 (C-4), 33.65 (C-23),
34.61 (C-18), 35.13 (C-7), 36.07 (C-19), 37.84 (C-10), 38.53
(C-8), 40.57 (C-1), 42.29 (C-3), 48.67 (C-9), 48.86 (C-17),
50.61 (C-14), 57.26 (C-5), 116.1 (C-12), 124.7 (C-22), 132.1
(C-21), 149.2 (C-13). EIMS, m/z 191 (100%), 204 (95), 396
(Mϩ, 52)
(60), 231 (26), 243 (26), 367 (21), 382 (Mϩ, 50). [α]D (CHCl3)
25
ϩ37.6 (c = 0.012).
33c (oil) in C6D6. δH 5.66 (m, H-21), 5.64 (m, H-22), 1.73 (3H,
d, J 6.6 Hz, H-29). δC 15.44 (C-28), 15.91 (C-25), 17.10 (C-26),
18.13 (C-29), 18.88 (C-2), 19.08 (C-6), 21.95 (C-24), 22.88
(C-27), 23.93 (C-11), 24.50 (C-16), 31.05 (C-20), 32.05 (C-15),
33.34 (C-4), 33.65 (C-23), 34.61 (C-18), 35.13 (C-7), 36.07
(C-19), 37.84 (C-10), 38.53 (C-8), 40.57 (C-1), 42.29 (C-3),
48.67 (C-9), 48.86 (C-17), 50.61 (C-14), 57.26 (C-5), 116.1
(C-12), 124.7 (C-22), 132.1 (C-21), 149.2 (C-13). Assignments
37 (solid) in C6D6. δH 0.88 (dd, J 12.0, 1.9, H-5), 0.93 (m,
H-1), 0.94 (3H,s, Me-28), 0.99 (6H, s, Me-24, Me-25), 1.03 (3H,
s, Me-23), 1.09 (3H, s, Me-26), 1.24 (3H,s, Me-27), 1.27 (m,
H-17), 1.30 (2H, m, H-3, H-15), 1.37 (m, H-16), 1.38 (m, H-7),
1.40 (m, H-13), 1.43 (4H, m, H-6, H-9, H-11), 1.45 (m, H-16),
1.50 (m, H-2), 1.51 (m, H-3), 1.55 (m, H-15), 1.57 (m, H-7), 1.63
(m, H-6), 1.65 (2H, m, H-12), 1.69 (m, H-19), 1.73 (m, H-2),
1.78 (m, H-1), 1.83 (m, H-22), 1.92 (m, H-22), 2.07 (dd, J 17, 3
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 1 4 5 6 – 1 4 7 0
1468