G. Gu et al. / Carbohydrate Research 346 (2011) 2406–2413
2411
40.1, 40.3, 40.7, 42.2, 56.4, 61.3 (2C), 62.2, 65.2, 65.6, 66.2, 66.9
(2C), 69.4 (2C), 69.5, 72.0, 73.2, 74.1, 74.2, 75.9, 81.0, 98.5, 99.5,
99.9, 109.7, 169.3, 169.4, 170.0, 170.1, 170.2; ESI-HRMS calcd for
3.74 (t, 1H, J 9.4 Hz, H-40), 3.92–4.04 (m, 5H, H-3, H-26b, H-6b0,
H-5b00, H-5b000), 4.36 (d, 1H, J 7.8 Hz, H-10), 4.40 (m, 1H, H-16),
4.55 (d, 1H, J 4.8 Hz, H-100), 4.58 (d, 1H, J 5.4 Hz, H-1000), 5.00–5.14
(m, 5H, H-30, H-200, H-2000, H-300, H-3000), 5.16–5.23 (m, 2H, H-400, H-
4000); 13C NMR (100 MHz, CDCl3): d 14.3, 16.1, 16.5, 20.6, 20.7,
20.8, 20.9, 21.1, 23.9, 25.8, 26.0, 26.5, 26.6, 27.1, 29.7, 30.5, 30.6,
31.8, 35.1, 35.3, 37.1, 40.2, 40.3, 40.7, 42.1, 56.4, 61.5, 62.2, 65.2,
65.6, 66.4, 66.6, 67.0, 69.1, 69.3, 69.5, 69.6, 72.8, 74.4, 74.7 (2C),
75.6, 81.0, 99.5, 99.6, 100.7, 109.7, 169.3, 169.4, 169.6, 170.1,
170.6; ESI-HRMS calcd for C57H88O23N: 1154.5742 (M+NH4)+;
found: 1154.5763; Anal. Calcd for C57H84O23: C, 60.20; H, 7.44.
Found: C, 60.41; H, 7.28.
C
59H86O24Na: 1201.5401 (M+Na)+; found: 1201.5366; Anal. Calcd
for C59H86O24: C, 60.09; H, 7.35. Found: C, 60.33; H, 7.18.
3.8.3. Sarsasapogenyl 2,3,4,6-tetra-O-acetyl-b-
(1?4)-[2,3,4,6-tetra-O-acetyl-b- -glucopyranosyl-(1?6)]-2,3-
di-O-acetyl-b- -glucopyranoside (18)
D-glucopyranosyl-
D
D
From compound 14 (118 mg) and sarsasapogenin 15 (42 mg) to
afford 18 (52 mg, 39%) as a white foam; ½a D25
ꢃ
ꢄ32 (c 3, CHCl3); 1H
NMR (400 MHz, CDCl3): d 0.75 (s, 3H, 18-CH3), 0.91 (s, 3H, 19-CH3),
0.98 (d, 3H, J 6.7 Hz, 21-CH3), 1.08 (d, 3H, J 7.0 Hz, 27-CH3), 1.98,
1.99, 2.01, 2.02, 2.03, 2.06, 2.08, 2.10 (8s, 10 ꢂ 3H, 10Ac), 3.30 (d,
1H, J 11.2 Hz, H-26a), 3.51 (m, 1H, H-50), 3.68 (t, 1H, J 9.4 Hz, H-
40), 3.68–3.74 (m, 2H, H-500, H-5000), 3.80 (dd, 1H, J 6.2, 11.2 Hz, H-
6a0), 3.95 (m, 2H, H-26b, H-6b0), 4.01–4.06 (m, 2H, H-3, H-6a00),
4.15 (dd, 1H, J 2.2, 12.4 Hz, H-6a000), 4.31 (dd, 1H, J 4.5, 12.4 Hz,
H-6b000), 4.35 (dd, 1H, J 4.6, 12.5 Hz, H-6b00), 4.38 (m, 1H, H-16),
4.47 (d, 1H, J 8.2 Hz, H-10), 4.50 (d, 1H, J 8.2 Hz, H-100), 4.66 (d,
1H, J 7.8 Hz, H-1000), 4.88 (dd, 1H, J 8.2, 9.8 Hz, H-20), 4.92 (dd, 1H,
J 8.2, 9.4 Hz, H-200), 5.00 (dd, 1H, J 7.8, 9.4 Hz, H-2000), 5.04 (t, 1H, J
9.6 Hz, H-400), 5.09 (t, 1H, J 9.6 Hz, H-4000), 5.13–5.20 (m, 3H, H-30,
H-300, H-3000); 13C NMR (100 MHz, CDCl3): d 14.3, 16.1, 16.5, 20.5,
20.6, 20.7, 20.9, 24.0, 25.8, 26.0, 26.5, 26.7, 27.1, 29.6, 30.3, 30.6,
31.8, 35.0, 35.3, 36.8, 40.1, 40.3, 40.7, 42.2, 56.4, 61.7, 61.9, 62.2,
65.2, 67.7, 68.0, 68.2, 71.4, 71.7 (2C), 71.8, 72.2, 72.5, 72.8, 74.1,
74.8, 76.3, 77.2, 81.0, 98.3, 100.4, 101.0, 109.7, 169.0, 169.2,
169.3, 169.4, 170.0, 170.2, 170.5, 170.6; ESI-HRMS calcd for
3.8.6. Sarsasapogenyl 2,3,4,6-tetra-O-acetyl-b-
(1?4)-[2,3,4,6-tetra-O-acetyl-b- -glucopyranosyl-(1?6)]-3-O-
acetyl-b- -glucopyranoside (21)
D-glucopyranosyl-
D
D
From compound 14 (118 mg) and sarsasapogenin 15 (42 mg) to
afford 21 (46 mg, 36%) as a white foam; ½a D25
ꢃ
ꢄ22 (c 1, CHCl3); 1H
NMR (400 MHz, CDCl3): d 0.75 (s, 3H, 18-CH3), 0.94 (s, 3H, 19-CH3),
0.99 (d, 3H, J 6.7 Hz, 21-CH3), 1.08 (d, 3H, J 7.0 Hz, 27-CH3), 1.98,
2.01, 2.02, 2.03, 2.06, 2.08, 2.10 (7s, 9 ꢂ 3H, 9Ac), 3.30 (d, 1H, J
10.8 Hz, H-26a), 3.42–3.53 (m, 2H, H-20, H-50), 3.67 (t, 1H, J
9.5 Hz, H-40), 3.67–3.74 (m, 2H, H-500, H-5000), 3.80 (dd, 1H, J 5.7,
11.2 Hz, H-6a0), 3.95 (dd, 1H, J 2.0, 10.8 Hz, H-26b), 4.00–4.08 (m,
3H, H-3, H-6b0, H-6a00), 4.15 (dd, 1H, J 2.0, 12.2 Hz, H-6a000), 4.23–
4.36 (m, 2H, H-6b00, H-6b000), 4.34 (d, 1H, J 7.8 Hz, H-10), 4.40 (m,
1H, H-16), 4.52 (d, 1H, J 8.0 Hz, H-100), 4.65 (d, 1H, J 7.8 Hz, H-1000),
4.92 (dd, 1H, J 8.0, 9.4 Hz, H-200), 5.00 (dd, 1H, J 7.8, 9.4 Hz, H-2000),
5.03–5.14 (m, 3H, H-30, H-400, H-4000), 5.15–5.22 (m, 2H, H-300, H-
3000); 13C NMR (100 MHz, CDCl3): d 14.3, 16.1, 16.5, 20.5, 20.6,
20.7, 20.8, 20.9, 24.0, 25.8, 26.0, 26.5, 26.6, 27.1, 29.7, 30.0, 30.6,
31.8, 35.1, 35.3, 37.1, 40.2, 40.3, 40.7, 42.2, 56.4, 61.8, 62.0, 62.2,
65.2, 68.0, 68.1, 68.3, 71.5, 71.8 (2C), 72.2, 72.6, 72.8, 72.9, 73.9,
74.8, 75.0, 76.0, 81.0, 100.1, 100.8, 101.1, 109.7, 169.0, 169.2,
169.3, 169.4, 170.1, 170.2, 170.4, 170.5; ESI-HRMS calcd for
C
65H94O28Na: 1345.5824 (M+Na)+; found: 1345.5815; Anal. Calcd
for C65H94O28: C, 58.99; H, 7.16. Found: C, 58.74; H, 7.40.
3.8.4. Sarsasapogenyl 2,3,4,6-tetra-O-acetyl-b-
(1?4)-[2,3,4-tri-O-acetyl- -arabinopyranosyl-(1?6)]-3-O-
acetyl-b- -glucopyranoside (19)
D-glucopyranosyl-
a-L
D
From compound 12 (110 mg) and sarsasapogenin 15 (42 mg) to
C
63H96O27N: 1298.6164 (M+NH4)+; found: 1298.6183; Anal. Calcd
for C63H92O27: C, 59.05; H, 7.24. Found: C, 59.26; H, 7.06.
afford 19 (41 mg, 34%) as a white foam; ½a D25
ꢃ
ꢄ26 (c 2, CHCl3); 1H
NMR (400 MHz, CDCl3): d 0.75 (s, 3H, 18-CH3), 0.94 (s, 3H, 19-CH3),
0.99 (d, 3H, J 6.7 Hz, 21-CH3), 1.08 (d, 3H, J 7.0 Hz, 27-CH3), 1.97,
2.01, 2.02, 2.07, 2.08, 2.12 (6s, 8 ꢂ 3H, 8Ac), 3.30 (d, 1H, J
11.0 Hz, H-26a), 3.40–3.49 (m, 2H, H-20, H-50), 3.66 (dd, 1H, J 2.8,
12.3 Hz, H-5a00), 3.71 (dd, 1H, J 3.2, 11.0 Hz, H-6a0), 3.72 (t, 1H, J
9.6 Hz, H-40), 3.79 (m, 1H, H-5000), 3.93–4.09 (m, 5H, H-3, H-26b,
H-5b00, H-6b0, H-6a000), 4.34 (d, 1H, J 7.8 Hz, H-10), 4.34–4.43 (m,
2H, H-16, H-6b000), 4.57 (d, 1H, J 8.0 Hz, H-1000), 4.61 (d, 1H, J
5.0 Hz, H-100), 4.92 (dd, 1H, J 8.0, 9.4 Hz, H-2000), 5.04–5.16 (m, 4H,
H-30, H-200, H-300, H-4000), 5.22 (t, 1H, J 9.4 Hz, H-3000), 5.26 (m, 1H,
H-400); 13C NMR (150 MHz, CDCl3): d 14.3, 16.0, 16.5, 20.5, 20.6,
20.7, 20.8, 20.9, 23.9, 25.7, 25.9, 26.5, 26.6, 27.1, 29.7, 30.2, 30.5,
31.7, 35.0, 35.3, 37.1, 40.1, 40.2, 40.6, 42.1, 56.4, 61.7, 62.1, 65.1,
65.5, 66.2, 66.8, 67.9, 69.1, 69.4, 71.6, 71.8, 72.7, 72.9, 73.9, 74.3,
75.0, 75.9, 81.0, 99.8, 100.3, 110.0, 109.7, 167.7, 168.9, 169.3,
3.8.7. Sarsasapogenyl 2,3,4,6-tetra-O-acetyl-b-
(1?4)-[2,3,4-tri-O-acetyl- -arabinopyranosyl-(1?6)]-3-O-
acetyl- -glucopyranoside (22)
D-glucopyranosyl-
a
-L
a
-D
From compound 12 (110 mg) and sarsasapogenin 15 (42 mg) to
afford 22 (18 mg, 15%) as a white foam; ½a D25
ꢃ
ꢄ48 (c 1, CHCl3); 1H
NMR (400 MHz, CDCl3): d 0.76 (s, 3H, 18-CH3), 0.97 (s, 3H, 19-CH3),
0.99 (d, 3H, J 6.7 Hz, 21-CH3), 1.08 (d, 3H, J 7.0 Hz, 27-CH3), 1.98,
2.01, 2.02, 2.05, 2.08, 2.09, 2.11, 2.13 (8s, 8 ꢂ 3H, 8Ac), 3.30 (d,
1H, J 11.0 Hz, H-26a), 3.54 (m, 1H, H-50), 3.64–3.82 (m, 5H, H-20,
H-40, H-6a0, H-5a00, H-5000), 3.90 (br d, 1H, J 11.0 Hz, H-26b), 3.92–
3.98 (m, 2H, H-3, H-5b00), 4.01–4.07 (m, 2H, H-6b0, H-6a000), 4.36–
4.45 (m, 2H, H-16, H-6b000), 4.56 (d, 1H, J 5.3 Hz, H-100), 4.60 (d,
1H, J 8.0 Hz, H-1000), 4.91 (d, 1H, J 3.6 Hz, H-10), 4.92 (dd, 1H, J 8.0,
10.0 Hz, H-2000), 5.03–5.10 (m, 2H, H-300, H-4000), 5.12–5.19 (m, 2H,
H-30, H-200), 5.23–5.28 (m, 2H, H-400, H-3000); ESI-HRMS calcd for
169.6, 170.1, 170.2, 170.5; ESI-HRMS calcd for
1226.5953 (M+NH4)+; found: 1226.5945; Anal. Calcd for
60H88O25: C, 59.59; H, 7.33. Found: C, 59.65; H, 7.56.
C60H92O25N:
C
60H88O25Na: 1231.5507 (M+Na)+; found: 1231.5489.
C
3.8.8. Sarsasapogenyl 2,3,4-tri-O-acetyl-
(1?4)-[2,3,4-tri-O-acetyl- -arabinopyranosyl-(1?6)]-3-O-
acetyl- -glucopyranoside (23)
a-L-arabinopyranosyl-
3.8.5. Sarsasapogenyl 2,3,4-tri-O-acetyl-
(1?4)-[2,3,4-tri-O-acetyl- -arabinopyranosyl-(1?6)]-3-O-
acetyl-b- -glucopyranoside (20)
a
-
L
-arabinopyranosyl-
a-L
a-
L
a-D
D
From compound 13 (103 mg) and sarsasapogenin 15 (42 mg) to
From compound 13 (103 mg) and sarsasapogenin 15 (42 mg) to
afford 23 (15 mg, 13%) as a white foam; ½a D25
ꢃ
ꢄ54 (c 1, CHCl3); 1H
afford 20 (40 mg, 35%) as a white foam; ½a D25
ꢃ
ꢄ28 (c 2, CHCl3); 1H
NMR (400 MHz, CDCl3): d 0.76 (s, 3H, 18-CH3), 0.97 (s, 3H, 19-CH3),
0.99 (d, 3H, J 6.7 Hz, 21-CH3), 1.08 (d, 3H, J 7.0 Hz, 27-CH3), 2.03,
2.07, 2.08, 2.09, 2.10, 2.12 (6s, 7 ꢂ 3H, 7Ac), 3.30 (d, 1H, J
11.0 Hz, H-26a), 3.51 (m, 1H, H-50), 3.62–3.78 (m, 5H, H-20, H-40,
H-6a0, H-5a00, H-5a000), 3.93–4.06 (m, 5H, H-3, H-26b, H-6b0, H-5b00,
H-5b000), 4.40 (m, 1H, H-16), 4.54 (d, 1H, J 5.2 Hz, H-100), 4.57 (d,
NMR (400 MHz, CDCl3): d 0.75 (s, 3H, 18-CH3), 0.94 (s, 3H, 19-
CH3), 0.99 (d, 3H, J 6.7 Hz, 21-CH3), 1.08 (d, 3H, J 7.0 Hz, 27-CH3),
2.03, 2.06, 2.07, 2.08, 2.09, 2.10, 2.11 (7s, 7 ꢂ 3H, 7Ac), 3.30 (d,
1H, J 11.0 Hz, H-26a), 3.38–3.50 (m, 2H, H-20, H-50), 3.63 (br d,
2H, J 12.2 Hz, H-5a00, H-5a000), 3.69 (dd, 1H, J 4.2, 11.0 Hz, H-6a0),