894
W. Seebacher et al.
ꢁ-D-Glucopyranosyl-(1!3)-ꢁ-D-glucopyranosyl-3O-oleanolic acid (1, randianin: C42H68O13)
The same procedure as described for 2 was used. 230 mg (0.19 mmol) 8 dissolved in 6 ml dry CHCl3
yielded after hydrogenation and preparative TLC (CH2Cl2:MeOH 8:2) 32 mg (22%) 1.
20
D
20
546
M.p.: 220ꢀC, (decomp.); Rf 0.34 (CH2Cl2:MeOH 8:2); ꢀ 13.2ꢀ, ꢀ 17.6ꢀ
(c 0.34, CH3OH); IR (KBr): ꢀv 3375 (s), 2928 (s), 1577 (s), 1459 (m), 1389 (m), 1077 (s), 890
(w), 827 (w), 789 (w), 649 (w), 621 (w), 472 (w) cmꢁ1; 1H NMR (400 MHz, ꢂ, CD3OD): 0.80±0.84
(m, 1H, 5-H), 0.89 (s, 3H, 24-H), 0.90 (s, 3H, 26-H), 0.93 (s, 3H, 29-H), 1.00 (s, 6H, 25-H, 30-H),
1.02±1.08 (m, 2H, 1-H, 15-H), 1.10 (s, 3H, 23-H), 1.19 (s, 3H, 27-H), 1.33±2.10 (m, 19H, 1-H, 2-H,
6-H, 7-H, 9-H, 11-H, 15-H, 16-H, 19-H, 21-H, 22-H), 2.93 (dd, J 13.0, 3.0 Hz, 1H, 18-H), 3.23
(dd, J 11.7, 4.2 Hz, 1H, 3-H), 3.32±3.36 (m, 1H, 50-H), 3.33 (t, J 9.9 Hz, 2H, 200-H, 400-H), 3.36±
3.40 (m, 1H, 500-H), 3.41 (t, J 9.9 Hz, 1H, 20-H), 3.44 (t, J 9.2 Hz, 1H, 300-H), 3.45 (t, J 8.9 Hz,
1H, 40-H), 5.58 (t, J 8.9 Hz, 1H, 30-H), 3.69 (dd, J 11.8, 5.8 Hz, 1H, 600-H), 3.74 (dd, J 12.0,
4.6 Hz, 1H, 60-H), 3.89 (dd, J 12.0, 2.1 Hz, 1H, 60-H), 3.93 (dd, J 11.8, 2.1 Hz, 1H, 600-H), 4.42
(d, J 7.9 Hz, 1H, 10-H), 4.62 (d, J 7.5 Hz, 1H, 100-H), 5.26 (s, 1H, 12-H) ppm; 13C NMR
(100 MHz, ꢂ, CD3OD): 16.26 (C-25), 17.33 (C-24), 18.36 (C-26), 19.67 (C-6), 24.52 (C-30), 24.69
(C-16), 24.86 (C-11), 26.78 (C-27), 27.27 (C-2), 28.84 (C-23), 29.40 (C-15), 32.03 (C-20), 34.12
(C-29), 34.41 (C-7), 34.52 (C-22), 35.61 (C-21), 38.22 (C-10), 40.09 (C-1), 40.45 (C-4), 40.85 (C-8),
43.26 (C-18), 43.51 (C-14), 48.14 (C-19), 49.45 (C-9), 57.38 (C-5), 62.79 (C-600), 62.98 (C-60), 70.37
(C-40), 71.79 (C-400), 75.36 (C-20), 75.75 (C-200), 77.55 (C-50), 78.01 (C-300), 78.42 (C-500), 88.27
(C-30), 91.19 (C-3), 105.52 (C-100), 106.56 (C-10), 123.14 (C-12), 146.47 (C-13), 184.95 (C-28) ppm;
MS (neg. LSIMS, 5 kV): m/z (%) 779 [M -H] (22.6), 763 (1.0), 659 (0.5), 645 (0.8), 617 (3.3), 551
(1.0), 483 (1.8), 455 (2.5), 437 (1.8), 367 (4.5), 275 (17.4), 276 (2.3), 205 (1.9), 183 (100.0), 119
(2.3), 91 (80.0), 71 (8.7), 45 (1.5).
Diphenylmethyl 20,30,60,200,300,400,600-heptaacetyl-ꢁ-D-glucopyranosyl-(1!4)-
ꢁ-D-glucopyranosyl-3O-oleanolate (9; C69H92O20)
1.3 g (2.1 mmol) 6 were dissolved in a mixture of 50 ml dry benzene and 50 ml dry nitromethane.
The solution was heated to 50ꢀC, and two thirds of the solvent were evaporated. Thereafter, 1.6 g
(6.3 mmol) Hg(CN)2 and 900 mg (1.3 mmol) acetobromocellobiose (obtained from octaacetylcello-
bioside [15, 17]) dissolved in 20 ml of benzene:CH3NO2 1:1 were added. The mixture was heated
under Ar to 100ꢀC and stirred for 3 h. After cooling to room temperature, CHCl3 was added, and the
solution was washed three times with 5% aqueous KJ, twice with 10% NaHCO3, and twice with
water. The organic phase was dried over Na2SO4 and evaporated. 2 g crude 9 were obtained and
puri®ed by CC with CH2Cl2: ethyl acetate 9:1 yielding 550 mg (34%) 9.
20
20
Rf 0.15 (CH2Cl2:ethyl acetate 9:1); ꢀ 7.3ꢀ, ꢀ 5.0ꢀ (c 0.2, CH3OH); IR
D
546
(KBr): ꢀv 2948 (m), 1758 (s), 1456 (w), 1367 (m), 1231 (s), 1159 (w), 1122 (w), 1038 (s), 700 (w)
1
cmꢁ1; UV (MeOH); ꢃ (log") 214 (4.412), 257 (4.064) nm; H NMR (400 MHz, ꢂ, CDCl3): 0.21
(s, 3H, 26-H), 0.61 (d, J 11.2 Hz, 1H, 5-H), 0.66 (s, 3H, 24-H), 0.75 (s, 3H, 25-H), 0.77±0.80 (m,
1H, 1-H), 0.83 (s, 3H, 23-H), 0.86 (s, 3H, 29-H), 0.89 (s, 3H, 30-H), 0.91±0.95 (m, 1H, 15-H), 1.04
(s, 3H, 27-H), 1.08±1.74 (m, 18H, 1-H, 2-H, 6-H, 7-H, 9-H, 11-H, 15-H, 16-H, 19-H, 21-H, 22-H),
1.93±2.00 (m, 1H, 16-H), 1.94 (s, 3H, COOCH3), 1.96 (s, 3H, COOCH3), 1.92 (s, 6H, 2 COOCH3),
1.99 (s, 3H, COOCH3), 2.04 (s, 3H, COOCH3), 2.05 (s, 3H, COOCH3), 2.91 (dd, J 13.6, 3.3 Hz,
1H, 18-H), 3.00 (dd, J 11.3, 4.5 Hz, 1H, 3-H), 3.50±3.55 (m, 1H, 50-H), 3.62 (ddd, J 9.8, 4.3,
2.3 Hz, 1H, 500-H), 3.67 (t, J 9.5 Hz, 1H, 40-H), 4.00 (d, J 12.4 Hz, 1H, 600-H), 4.06 (dd, J 11.9,
5.7 Hz, 1H, 60-H), 4.31 (dd, J 12.4, 4.3 Hz, 1H, 600-H), 4.42±4.45 (m, 1H, 60-H), 4.44 (d, J 8.3 Hz,
1H, 10-H), 4.46 (d, J 8.6 Hz, 1H, 100-H), 4.88 (t, J 8.6 Hz, 1H, 200-H), 4.89 (dd, J 9.3, 8.3 Hz,
1H, 20-H), 5.01 (t, J 9.7 Hz, 1H, 400-H), 5.10 (t, J 9.3 Hz, 1H, 300-H), 5.13 (t, J 9.3 Hz, 1H,
30-H), 6.78 (s, 1H, CHPh2), 7.19±7.30 (m, 10H, aromatic H) ppm; 13C NMR (100 MHz, ꢂ, CDCl3):
15.07 (C-25), 16.24 (C-24), 16.47 (C-26), 18.02 (C-6), 20.44 (3 COOCH3), 20.48, 20.54, 20.62,