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HETEROCYCLES, Vol. 74, 2007
mixture was extracted three times with CHCl . The combined extract was washed with brine, dried over
3
MgSO , and evaporated. The crude product was chromatographed on silica gel (10% MeOH in CHCl ) to
4
3
give 113.2 mg (83%) of 18 as a pale yellowish amorphous powder, a portion of which was recrystallized
from acetone and n-hexane to give colorless prisms (mp 231–234 °C). Compound 18: UV (MeOH) λmax
-
1
1
nm: 292, 265, 239, 222, 205. IR (KBr) νmax cm : 3381, 2924, 1726, 1616, 1468. H NMR (500 MHz,
CDCl ) δ ppm: 7.17 (1H, d, J=6.8 Hz, H-9), 7.13 (1H, ddd, J=7.6, 7.6, 1.3 Hz, H-11), 6.87 (1H, dd, J=7.3,
3
7
.3 Hz, H-10), 6.72 (1H, d, J=7.8 Hz, H-12), 4.19 (1H, br s, N -H), 4.18 (1H, m, H-17), 3.87 (2H, m, H-1’,
a
overlapped with H-2’), 3.76 (3H, s, 22-OCH ), 3.60 (1H, d, J=9.3 Hz, H-1’), 3.42 (1H, d, J=9.5 Hz, H-2’),
3
3
.27 (1H, br s, 17-OH), 2.88 (1H, dd, J=11.1, 3.1 Hz, H-21), 2.61 (1H, d, J=11.5 Hz, H-3), 2.57 (1H, m,
H-5), 2.42 (1H, ddd, J=12.3, 12.3, 2.4 Hz, H-5), 2.31 (1H, dd, J=11.1, 1.8 Hz, H-16), 2.02 (1H, dd,
J=10.9, 10.9 Hz, H-21), 1.99 (1H, m, H-18), 1.90 (3H, m, H-6, overlapped with H-14 and H-15), 1.77
(
1H, ddd, J=13.8, 13.8, 4.4 Hz, H-6), 1.50 (3H, m, H-18, overlapped with H-19 and H-20), 1.39 (1H, m,
1
3
H-19), 1.24 (1H, ddd, J=12.1, 12.1, 12.1 Hz, H-14). C-NMR (100 MHz, CDCl ) δ ppm: 176.1 (C-22),
3
1
6
4
46.6 (C-13), 130.7 (C-8), 128.7 (C-11), 122.1 (C-9), 120.1 (C-10), 111.8 (C-12), 90.9 (C-2), 80.2 (C-7),
6.6 (C-17), 61.9 (C-1’), 61.8 (C-21), 61.3 (C-2’), 59.2 (C-3), 52.3 (C-16), 51.9 (22-OCH ), 50.1 (C-5),
3
25
0.3 (C-20), 37.4 (C-6), 36.8 (C-15), 31.1 (C-18), 29.3 (C-14), 23.2 (C-19). [α]D -44 (c 0.98, CHCl ).
3
+
FAB-MS (NBA) m/z: 415 [M+H] . HR-FAB-MS (NBA/PEG): calcd. for C H N O : 415.2233, found:
2
3
31
2
5
4
15.2202.
Under the reaction conditions above without the addition of NH Cl, compound 19 was obtained in 35%
4
-
1
yields. Compound 19: UV (MeOH) λmax nm: 297, 242, 206. IR (KBr) νmax cm : 3399, 2927, 1727, 1615.
1
H NMR (500 MHz, CDCl ) δ ppm: 7.20 (1H, ddd, J=7.4, 7.4, 1.2 Hz, H-9), 7.19 (1H, d, J=7.6 Hz, H-11),
3
6
2
.83 (1H, ddd, J=7.5, 7.5, 0.8 Hz, H-10), 6.76 (1H, dd, J=8.4, 1.1 Hz, H-12), 4.34 (1H, ddd, J=11.6, 11.6,
.8 Hz, H-2’), 4.16 (1H, m, H-17), 4.07 (1H, br s, N -H), 4.02 (1H, ddd, J=11.9, 11.9, 2.8 Hz, H-1’), 3.78
a
(
3H, s, 16-CO CH ), 3.63 (1H, dd, J=11.4, 2.4 Hz, H-2’), 3.49 (1H, dd, J=11.9, 2.4 Hz, H-1’), 2.83 (1H,
2 3
m, H-5), 2.80 (1H, dd, J=11.8, 2.6 Hz, H-21), 2.66 (1H, ddd, J=13.4, 13.4, 4.8 Hz, H-6), 2.28 (1H, dd,
J=11.3, 2.1 Hz, H-16), 2.12 (1H, ddd, J=13.7, 2.4, 2.4 Hz, H-6), 1.98 (1H, ddd, J=12.5, 12.5, 2.6 Hz,
H-5), 1.91 (1H, dd, J=13.7, 3.1 Hz, H-18), 1.83 (1H, dd, J=10.8, 2.6 Hz, H-3), 1.66 (2H, overlapped,
H-15, and H-21), 1.58 (1H, m, H-14), 1.50 (1H, m, H-18), 1.46 (1H, ddd, J=12.7, 2.7, 2.7 Hz, H-14),
1
3
1
.38-1.34 (2H, overlapped, H-19, and H-20), 1.31-1.26 (1H, m, H-19). C NMR (125 MHz, CDCl ) δ
3
ppm: 175.6 (16-CO CH ), 148.4 (C-13), 130.2 (C-9), 129.1 (C-8), 123.0 (C-11), 119.6 (C-10), 111.1
2
3
(
C-12), 92.0 (C-2), 75.6 (C-7), 68.0 (C-3), 66.8 (C-17), 61.7 (C-21), 60.6 (C-2’), 58.1 (C-1’), 53.1 (C-5),
2.4 (C-16), 51.9 (16-CO CH ), 39.7 (C-20), 35.7 (C-15), 31.3 (C-18), 28.7 (C-14), 23.7 (C-6), 23.0
5
2
3
+
(
C-19). EI-MS m/z (%): 414 (M , 67), 225 (100). HR-EI-MS: calcd. for C H N O : 414.2154, found:
23 30 2 5
4
14.2142.