J Nat Med (2013) 67:590–598
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Compound 9
Compound 12
Amorphous powder; [a]2D6 -11.8 (c = 0.10, MeOH); IR
(film) mmax cm-1: 3288 (OH), 2770 (CH); 1H-NMR
(C5D5N, 500 MHz) d: 4.75 (1H, ddd, J = 7.2, 7.2, 4.4 Hz,
H-16), 4.32 (1H, br s, W1/2 = 5.7 Hz, H-12), 4.12 (1H, m,
Amorphous powder; [a]2D2 -26.0 (c = 0.10, MeOH); IR
(film) mmax cm-1: 3371 (OH), 2929 (CH); 1H-NMR
(C5D5N, 500 MHz) d: 5.42 (1H, br d, J = 5.5 Hz, H-6),
5.06 (1H, d, J = 7.7 Hz, H-10), 4.76 (1H, ddd, J = 7.4, 7.0,
4.4 Hz, H-16), 4.52 (1H, overlapping, H-22), 4.30 (1H,
overlapping, H-11), 4.01 (1H, overlapping, H-3), 3.87 (1H,
m, H-24), 1.27 (3H, s, Me-19), 1.21 (3H, d, J = 7.3 Hz,
Me-21), 1.20 (3H, s, Me-18), 1.06 (3H, d, J = 6.8 Hz,
Me-27), 1.02 (3H, d, J = 6.8 Hz, Me-26); 13C-NMR
(C5D5N, 125 MHz): Table 1; HR-ESITOFMS (m/z):
613.3969 [M ? H]? (calc. for C33H57O10, 613.3952).
H-23), 4.05 (1H, br d, J = 2.0 Hz, H-6), 3.95 (1H, m, W1/2
=
22.1 Hz, H-3), 3.67 (1H, dd, J = 6.4, 4.7 Hz, H-24), 2.38
(1H, dd, J = 11.3, 7.2 Hz, H-17), 1.90 (1H, m, H-11eq), 1.89
(1H, m, H-11ax), 1.47 (3H, d, J = 6.6 Hz, Me-21), 1.44 (3H,
s, Me-19), 1.27 (3H, d, J = 6.7 Hz, Me-26), 1.26 (3H, s, Me-
18), 1.11 (3H, d, J = 6.9 Hz, Me-27); 13C-NMR (C5D5N,
125 MHz): Table 1; HR-ESITOFMS (m/z): 469.3511
[M ? H]? (calc. for C27H49O6, 469.3529).
Compound 12a
Compound 10
Amorphous powder; [a]2D5 -6.6 (c = 0.04, MeOH); IR (film)
mmax cm-1: 3346 (OH), 2924 (CH); 1H-NMR (C5D5N,
500 MHz) d: 5.52 (1H, br d, J = 5.3 Hz, H-6), 4.78 (1H, ddd,
J = 7.5, 7.5, 4.6 Hz, H-16), 4.54 (1H, m, H-22), 4.39 (1H,
Amorphous powder; [a]2D3 -16.4 (c = 0.10, MeOH); IR
(film) mmax cm-1: 3375 (OH), 2932 (CH), 1708 (C=O); 1H-
NMR (C5D5N, 500 MHz) d: 5.06 (1H, d, J = 7.7 Hz,
H-10), 4.57 (1H, ddd, J = 7.4, 7.0, 4.8 Hz, H-16), 4.09 (1H,
overlapping, H-23), 3.99 (1H, overlapping, H-3), 3.69 (1H,
dd, J = 11.0, 5.3 Hz, H-24), 1.19 (3H, d, J = 6.6 Hz, Me-
21), 0.66 (3H, s, Me-19), 1.28 (3H, d, J = 6.7 Hz, Me-26),
1.17 (3H, d, J = 6.9 Hz, Me-27), 1.00 (3H, s, Me-18), 0.66
(3H, s, Me-19); 13C-NMR (C5D5N, 125 MHz): Table 1;
HR-ESITOFMS (m/z): 635.3766 [M ? Na]? (calc. for
C33H56O10Na, 635.3771).
ddd, J = 10.6, 10.6, 4.8 Hz, H-11), 3.93 (1H, m, W1/2
=
21.7 Hz, H-3), 3.88 (1H, m, H-24), 2.75 (1H, overlapping,
H-4ax), 2.62 (1H, m, H-20), 2.02 (1H, m, H-23a), 1.81 (1H,
m, H-23b), 1.78 (1H, dd, J = 11.2, 7.5 Hz, H-17), 1.63 (1H,
overlapping, H-8), 1.53 (1H, overlapping, H-1ax), 1.43 (3H,
s, Me-19), 1.37 (1H, dd, J = 10.6, 10.1 Hz, H-9), 1.26 (3H, s,
Me-18), 1.24 (3H, d, J = 7.1 Hz, Me-21), 1.12 (1H, over-
lapping, H-14), 1.08 (3H, d, J = 6.8 Hz, Me-26), 1.04(3H, d,
J = 6.8 Hz, Me-27); 13C-NMR (C5D5N, 125 MHz):
Table 1; HR-ESITOFMS (m/z): 473.3202 [M ? Na]? (calc.
for C27H46O5Na, 473.3243).
Compound 10a
Amorphous powder; [a]2D5 ?8.4 (c = 0.04, MeOH); IR (film)
mmax cm-1: 3375 (OH), 2924 (CH), 1714 (C=O); CD kmax
(MeOH) nm (De): 294 (-13.6); HR-ESITOFMS (m/z):
473.3244 [M ? Na]? (calc. for C27H46O5Na, 473.3243).
Compound 13
Amorphous powder; [a]2D5 -12.4 (c = 0.10, MeOH); IR
(film) mmax cm-1: 3371 (OH), 2929 (CH); 1H-NMR
(C5D5N, 500 MHz) d: 5.51 (1H, br d, J = 6.7 Hz, H-6),
5.17 (1H, br s, H-26a), 4.93 (1H, br s, H-26b), 4.93 (1H, d,
J = 7.9 Hz, H-10), 4.57 (1H, ddd, J = 7.5, 7.5, 4.4 Hz,
H-16), 4.47 (1H, m, H-24), 4.36 (1H, ddd, J = 10.3, 10.3,
4.5 Hz, H-11), 3.93 (1H, m, W1/2 = 21.7 Hz, H-3), 1.87
(3H, s, Me-27), 1.41 (3H, s, Me-19), 1.21 (3H, d,
J = 7.3 Hz, Me-21), 1.19 (3H, s, Me-18); 13C-NMR
(C5D5N, 125 MHz): Table 1; HR-ESITOFMS (m/z):
617.3690 [M ? Na]? (calc. for C33H54O9Na, 617.3666).
Compound 11
Amorphous powder; [a]2D5 ?21.9 (c = 0.10, MeOH); IR
(film) mmax cm-1: 3377 (OH), 2929 (CH), 1702 (C=O); CD
1
kmax (MeOH) nm (De): 294 (-6.84); H-NMR (C5D5N,
500 MHz) d: 4.62 (1H, ddd, J = 7.1, 7.1, 4.6 Hz, H-16),
4.22 (1H, ddd, J = 10.4, 10.4, 4.9 Hz, H-11), 4.08 (1H, m,
H-23), 3.90 (1H, m, W1/2 = 22.1 Hz, H-3), 3.68 (1H, dd,
J = 6.4, 4.7 Hz, H-24), 2.62 (1H, dd, J = 12.2, 4.9 Hz,
H-12eq), 1.65 (1H, dd, J = 10.4, 10.4 Hz, H-9), 1.60 (1H,
dd, J = 12.2, 10.4 Hz, H-12ax), 1.27 (3H, d, J = 6.7 Hz,
Me-26), 1.19 (3H, d, J = 6.6 Hz, Me-21), 1.15 (3H, d,
J = 6.9 Hz, Me-27), 1.07 (3H, s, Me-18), 1.07 (3H, s,
Me-19); 13C-NMR (C5D5N, 125 MHz): Table 1; HR-ESI-
TOFMS (m/z): 467.3372 [M ? H]? (calc. for C27H47O6,
467.3373).
Compound 13a
Amorphous powder; [a]2D3 ?6.6 (c = 0.10, MeOH); IR
(film) mmax cm-1: 3357 (OH), 2926 (CH); 1H-NMR
(C5D5N, 500 MHz) d: 5.52 (1H, br d, J = 5.6 Hz, H-6),
5.24 (1H, br s, H-26a), 4.93 (1H, br s, H-26b), 4.62 (1H,
ddd, J = 7.6, 7.2, 4.6 Hz, H-16), 4.44 (1H, dd, J = 8.6,
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