X. Ma et al. / Carbohydrate Research 329 (2000) 495–505
501
1
65.3, 56.8, 56.2, 55.3, 50.2, 43.2, 39.8, 39.5,
38.7, 37.3, 36.7, 36.2, 35.8, 31.9, 29.7, 29.3,
28.2, 28.0, 24.3, 23.8, 22.8, 22.5, 21.0, 20.8,
19.3, 18.7, 11.8, 6.8, 5.0, 4.8. ESIMS (m/z):
−5.2° (c 0.82, CHCl3). H NMR (300 MHz,
CDCl3): l 7.94 (d, 2 H, J 8.8 Hz), 6.92 (d, 2
H, J 8.8 Hz), 4.95 (dd, 2 H, J 12.1, 6.6 Hz),
4.66 (d, 1 H, J 6.4 Hz), 4.35 (d, 1 H, J 5.5 Hz),
4.42–4.18 (m, 1 H), 4.06 (t, 1 H, J 5.7 Hz),
3.97 (m, 2 H), 3.84 (s, 3 H), 3.66 (m, 3 H),
3.48–3.28 (m, 4 H), 3.18 (dd, 1 H, J 10.7, 8.0
Hz), 1.89 (s, 3 H). 13C NMR (75 MHz,
CDCl3): 169.0, 164.5, 163.2, 131.9, 123.0,
113.3, 109.2, 101.5, 98.8, 80.8, 75.1, 73.5, 71.5,
68.8, 66.8, 65.2, 62.2, 56.3, 55.4, 54.4, 44.7,
41.6, 40.6, 40.0, 37.0, 35.7, 35.1, 34.3, 23.3,
31.8, 31.4, 30.3, 29.1, 28.8, 21.0, 20.9, 17.1,
16.5, 14.5, 12.3, 6.8, 5.0, 4.8. ESIMS (m/z):
1222 [M+Na+].
1193
[M+Na+].
Anal.
Calcd
for
C65H112O12Si3: C, 66.73; H, 9.65. Found: C,
66.85; H, 9.88.
26-Deoxydihydrodiosgenin-3-yl 2-O-(4-meth-
oxybenzoyl)-3,4-di-O-triethylsilyl-i- -xylo-
D
pyranosyl-(13)-2-O-acetyl-3-O-triethylsilyl-
h- -arabinopyranoside (30): A white foam (56
L
mg, 64%); Rf 0.75 (8:1 petroleum ether–
1
EtOAc). [h]2D1 −19.7° (c 1.75, CHCl3). H
NMR (300 MHz, CDCl3): l 7.99 (d, 2 H, J
8.8 Hz), 6.90 (d, 2 H, J 8.8 Hz), 5.26 (m, 1 H),
4.98 (t, 2 H, J 7.4 Hz), 4.69 (d, 1 H, J 6.7 Hz),
4.52 (d, 1 H, J 6.8 Hz), 4.27 (m, 2 H), 3.91 (m,
2 H), 3.86 (s, 3 H), 3.81 (m, 1 H), 3.70 (m, 3
H), 3.38–3.23 (m, 3 H), 3.21 (dd, 1 H, J 11.4,
8.0 Hz), 1.88 (s, 3 H). 13C NMR (75 MHz,
CDCl3): 169.0, 164.5, 163.2, 140.9, 131.9,
123.0, 121.3, 113.3, 101.5, 99.2, 90.5, 83.1,
78.1, 75.2, 73.6, 71.6, 71.3, 65.3, 57.0, 55.3,
50.2, 40.7, 39.5, 38.6, 37.9, 37.3, 36.9, 35.9,
32.3, 32.0, 31.6, 31.4, 29.7, 29.3, 28.3, 22.5,
22.4, 20.8, 20.6, 19.4, 19.0, 16.4, 6.8, 5.1, 5.0,
4.8.
Hecogenin-3-yl 2-O-(4-methoxybenzoyl)-3,
4-di-O-triethylsilyl-i-
D
-xylopyranosyl-(13)-
-arabinopyran-
2-O-acetyl-3-O-triethylsilyl-h-
L
oside (28): Rf 0.33 (10:1 petroleum ether–
EtOAc). [h]2D1 +8.5° (c 0.56, CHCl3). 1H
NMR (300 MHz, CDCl3): l 7.95 (d, 2 H, J
8.8 Hz), 6.88 (d, 2 H, J 8.8 Hz), 4.93 (dd, 2 H,
J 13.7, 6.6 Hz), 4.66 (d, 1 H, J 6.3 Hz), 4.34
(d, 1 H, J 5.5 Hz), 4.39–4.24 (m, 1 H), 4.19 (t,
1 H, J 5.0 Hz), 4.14–3.94 (m, 2 H), 3.84 (s, 3
H), 3.76–3.60 (m, 3 H), 3.50–3.26 (m, 4 H),
3.19 (dd, 1 H, J 10.4, 8.0 Hz), 1.86 (s, 3 H).
13C NMR (75 MHz, CDCl3): 213.5, 169.0,
164.5, 163.2, 131.9, 130.8, 128.8, 123.0, 113.3,
109.2, 101.3, 79.2, 74.9, 73.4, 71.4, 71.3, 68.5,
68.1, 66.9, 65.1, 55.8, 55.6, 55.3, 55.0, 53.5,
44.6, 42.2, 37.8, 36.5, 36.2, 34.3, 34.1, 31.6,
31.4, 31.1, 30.4, 30.2, 28.9, 28.8, 28.4, 23.8,
20.8, 17.1, 16.0, 14.0, 13.2, 11.8, 10.9, 6.8, 5.0,
4.8. ESIMS (m/z): 1214 [M+Na+]. Anal.
Calcd for C65H108O15Si3: C, 64.32; H, 8.97.
Found: C, 64.74; H, 9.04.
Dehydroisoandrosterone-3-yl 2-O-(4-meth-
oxybenzoyl)-3,4-di-O-triethylsilyl-i- -xylo-
D
pyranosyl-(13)-2-O-acetyl-3-O-triethylsilyl-
h- -arabinopyranoside (31): A white foam (43
L
mg, 54%); Rf 0.71 (10:1 petroleum ether–
EtOAc). [h]2D1 +3.9° (c 1.82, CHCl3). 1H
NMR (300 MHz, CDCl3): l 7.98 (d, 2 H, J
8.5 Hz), 6.90 (d, 2 H, J 8.5 Hz), 5.26 (m, 1 H),
4.97 (t, 2 H, J 7.6 Hz), 4.72 (d, 1 H, J 5.1 Hz),
4.38 (d, 1 H, J 5.8 Hz), 4.00 (m, 2 H),
3.93–3.63 (m, 5 H), 3.83 (s, 3 H), 3.40–3.25
(m, 2 H), 3.22 (dd, 1 H, J 11.3, 7.9 Hz), 1.88
(s, 3 H). 13C NMR (75 MHz, CDCl3): 221.0,
169.0, 164.5, 163.2, 141.0, 131.8, 122.9, 120.8,
113.3, 101.4, 99.1, 78.1, 75.1, 73.6, 71.4, 71.2,
68.1, 65.2, 55.3, 51.8, 50.3, 47.5, 38.7, 37.2,
36.8, 35.8, 31.4, 30.8, 30.3, 29.3, 28.9, 23.7,
22.9, 21.8, 20.8, 20.3, 19.3, 14.0, 13.5, 10.9,
6.8, 5.0, 4.8. ESIMS (m/z): 1095 [M+Na+].
Anal. Calcd for C57H94O13Si3·3.5 H2O: C,
60.33; H, 8.97. Found: C, 60.27; H, 8.88.
(Z)-5,17(20)-Pregnadiene-3-yl 2-O-(4-meth-
Cholesterol-3-yl 2-O-(4-methoxybenzoyl)-3,
4-di-O-triethylsilyl-i-
D
-xylopyranosyl-(13)-
-arabinopyra-
2-O-acetyl-3-O-triethylsilyl-h-
L
noside (29): A white foam (58 mg, 67%); Rf
0.85 (10:1 petroleum ether–EtOAc). [h]D21
−
1
7.0° (c 3.43, CHCl3). H NMR (300 MHz,
CDCl3): l 7.97 (d, 2 H, J 8.8 Hz), 6.90 (d, 2
H, J 8.8 Hz), 5.26 (m, 1 H), 5.00 (m, 2 H),
4.69 (d, 1 H, J 6.4 Hz), 4.36 (d, 1 H, J 5.8 Hz),
4.10–3.55 (m, 5 H), 3.86 (s, 3 H), 3.48–3.25
(m, 2 H), 3.21 (dd, 1 H, J 11.3, 7.8 Hz), 1.88
(s, 3 H). 13C NMR (75 MHz, CDCl3): 69.0,
164.5, 163.2, 140.9, 131.9, 123.0, 121.5, 113.3,
101.5, 99.1, 78.3, 75.2, 73.6, 71.6, 71.4, 68.9,
oxybenzoyl)-3,4-di-O-triethylsilyl-i-
D
-xylo-
pyranosyl-(13)-2-O-acetyl-3-O-triethylsilyl-