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A. Presser et al.
(m, H-60a), 3.68 (m, H-60b), 3.63 (t, J ¼ ꢄ8 Hz, H-40), 3.57 (m, H-20), 3.55 (m, H-3), 2.43 (m, H-4a), 2.29
(m, H-4b), 2.04 (m, H-2a), 2.00 (m, H-12a), 1.97 (m, H-7a), 1.87 (m, H-1a), 1.83 (m, H-16a), 1.57 (m,
H-15a), 1.56 (m, H-2b), 1.54 (m, H-7b), 1.52 (m, H-25), 1.49 (m, H-11a), 1.46 (m, H-11b), 1.44 (m, H-
8), 1.39 (m, H-20), 1.33 (m, H-22a, H-23a), 1.26 (m, H-16b), 1.17 (m, H-12b), 1.14 (m, H-23b), 1.12 (m,
H-24a), 1.10 (m, H-17, H-24b), 1.06 (m, H-15b), 1.05 (m, H-1b), 1.02 (s, H-19), 1.00 (m, H-22b), 0.99
(m, H-14), 0.92 (m, H-9), 0.92 (d, J ¼ 6.6Hz, H-21), 0.87 (d, J ¼ 6.6Hz, H-26, H-27), 0.68 (s, H-18)
ppm; 13C NMR (150 MHz, CDCl3): ꢂ ¼ 140.9 (C-5), 138.7–127.5 (aromatic C), 121.7 (C-6), 94.6 (C-
10), 82.1 (C-30), 79.6 (C-20), 78.0 (C-3), 77.9 (C-40), 75.8–73.2 (4ꢃPhCH2), 70.0 (C-50), 68.6 (C-60),
56.8 (C-14), 56.2 (C-17), 50.2 (C-9), 42.3 (C-13), 39.9 (C-4), 39.8 (C-12), 39.2 (C-24), 37.3 (C-1), 36.5
(C-10), 36.2 (C-22), 35.8 (C-20), 32.0 (C-7), 31.9 (C-8), 30.0 (C-2), 28.2 (C-16), 28.0 (C-25), 24.3 (C-
ꢀ
ꢀ
15), 23.8 (C-23), 22.8 (C-27), 22.6 (C-26), 21.1 (C-11), 19.2 (C-19), 18.7 (C-21), 11.9 (C-18) ppm.
1
12b: H NMR (600MHz, CDCl3): ꢂ ¼ 7.36–7.12 (m, aromatic H), 5.34 (s, H-6), 5.01–4.46 (m,
4ꢃPhCH2), 4.50 (d, J ¼ ꢄ8 Hz, H-10), 3.73 (m, H-60a), 3.68 (m, H-60b), 3.63 (t, J ¼ ꢄ9 Hz, H-30), 3.55
(t, J ¼ 8.8 Hz, H-40), 3.48 (m, H-3), 3.46 (m, H-50), 3.44 (t, J ¼ 8.7 Hz, H-20), 2.40 (m, H-4a), 2.35 (m,
H-4b), 2.04 (m, H-2a), 2.00 (m, H-12a), 1.97 (m, H-7a), 1.87 (m, H-1a), 1.83 (m, H-16a), 1.57 (m, H-
15a), 1.56 (m, H-2b), 1.54 (m, H-7b), 1.52 (m, H-25), 1.49 (m, H-11a), 1.46 (m, H-11b), 1.44 (m, H-8),
1.39 (m, H-20), 1.33 (m, H-22a, H-23a), 1.26 (m, H-16b), 1.17 (m, H-12b), 1.14 (m, H-23b), 1.12 (m, H-
24a), 1.10 (m, H-17, H-24b), 1.06 (m, H-15b), 1.05 (m, H-1b), 1.02 (s, H-19), 1.00 (m, H-22b), 0.99 (m,
H-14), 0.92 (m, H-9), 0.92 (d, J ¼ 6.6 Hz, H-21), 0.87 (d, J ¼ 6.6 Hz, H-26, H-27), 0.68 (s, H-18) ppm;
13C NMR (150 MHz, CDCl3): ꢂ ¼ 140.7 (C-5), 138.7–127.5 (aromatic C), 121.9 (C-6), 102.3 (C-10),
84.8 (C-30), 82.4 (C-20), 78.0 (C-40), 76.7 (C-3), 75.8–73.2 (4ꢃPhCH2), 74.8 (C-50), 69.1 (C-60), 56.8
(C-14), 56.2 (C-17), 50.2 (C-9), 42.3 (C-13), 39.8 (C-12), 39.2 (C-4, C-24), 37.3 (C-1), 36.5 (C-10),
36.2 (C-22), 35.8 (C-20), 32.0 (C-7), 31.9 (C-8), 30.0 (C-2), 28.2 (C-16), 28.0 (C-25), 24.3 (C-15), 23.8
ꢀ
ꢀ
(C-23), 22.8 (C-27), 22.6 (C-26), 21.1 (C-11), 19.4 (C-19), 18.7 (C-21), 11.9 (C-18) ppm.
Cholesteryl ꢀ,ꢁ-D-glucopyranoside (13)
The compound was prepared from 12 by treatment with cyclohexene and 20% palladium hydroxide on
carbon as described in Ref. [40]. Purification was performed on a silica gel column using EtOAc=EtOH
(2=1) yielding the anomers 13a and 13b as white solids (83%, ratio 3:2). The data agree with those of
1
Ref. [44]. However, the accurate H and 13C NMR data could be assigned.
1
13a: Mp 206–208ꢁC, Rf ¼ 0.30 (EtOAc=EtOH¼ 2=1); H NMR (600 MHz, DMSO-d6): ꢂ ¼ 5.29
(s, H-6), 4.78 (d, J ¼ 3.5Hz, H-10), 4.43 (m, H-60a), 3.59 (d, J ¼ 9.6Hz, H-60b), 3.45 (m, H-50), 3.39 (m,
H-30), 3.36 (m, H-3), 3.15 (dd, J ¼ 9.0, 3.6 Hz, H-20), 3.04 (t, J ¼ 9.6 Hz, H-40), 2.34 (m, H-4a), 2.24
(m, H-4b), 1.96 (m, H-12a), 1.92 (m, H-7a), 1.86 (m, H-2a), 1.80 (m, H-1a), 1.79 (m, H-16), 1.54 (m, H-
15a), 1.50 (m, H-25), 1.49 (m, H-7b), 1.48 (m, H-11a), 1.40 (m, H-8, H-11b), 1.38 (m, H-2b), 1.35 (m,
H-20), 1.32 (m, H-22a), 1.31 (m, H-23a), 1.22 (m, H-16b), 1.14 (m, H-12b, H-23b), 1.11 (m, H-24a, H-
24b), 1.08 (m, H-17), 1.05 (m, H-15b), 0.98 (m, H-1b, H-22b), 0.97 (m, H-14), 0.96 (s, H-19), 0.90
(d, J ¼ 6.6 Hz, H-21), 0.89 (m, H-9), 0.84 (d, J ¼ 6.6 Hz, H-26, H-27), 0.65 (s, H-18) ppm; 13C NMR
(150 MHz, DMSO-d6): ꢂ ¼ 140.6 (C-5), 121.0 (C-6), 96.8 (C-10), 76.3 (C-3), 73.1 (C-30), 72.8 (C-50),
71.8 (C-20), 70.1 (C-40), 60.9 (C-60), 56.1 (C-14), 55.5 (C-17), 49.5 (C-9), 41.8 (C-13), 39.6 (C-4), 39.2
(C-12), 38.8 (C-24), 36.5 (C-1), 36.1 (C-10), 35.5 (C-22), 35.1 (C-20), 31.3 (C-7, C-8), 27.7 (C-16),
ꢀ
ꢀ
27.4 (C-2), 27.3 (C-25), 23.8 (C-15), 23.1 (C-23), 22.6 (C-27), 22.3 (C-26), 20.5 (C-11), 19.0
(C-19), 18.5 (C-21), 11.6 (C-18) ppm.
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13b: Mp 258–260ꢁC, Rf ¼ 0.38 (EtOAc=EtOH ¼ 2=1); H NMR (600 MHz, DMSO-d6): ꢂ ¼ 5.32
(s, H-6), 4.21 (d, J ¼ 7.8 Hz, H-10), 3.65 (dd, J ¼ 11.4, 6.0 Hz, H-60a), 3.46 (m, H-3), 3.41 (d,
J ¼ 11.4Hz, H-60b), 3.13 (t, J ¼ 9.0 Hz, H-30), 3.07 (m, H-50), 3.03 (t, J ¼ 9.0Hz, H-40), 2.90 (m, H-
20), 2.36 (m, H-4a), 2.14 (m, H-4b), 1.96 (m, H-12), 1.92 (m, H-7a), 1.82 (m, H-2a), 1.79 (m, H-1a), 1.78
(m, H-16a), 1.54 (m, H-15a), 1.50 (m, H-25), 1.49 (m, H-7b, H-11a), 1.48 (m, H-2b), 1.40 (m, H-8,
H-11b), 1.34 (m, H-20), 1.31 (m, H-22a, H-23a), 1.23 (m, H-16b), 1.14 (m, H-12b), 1.13 (m, H-23b),
1.11 (m, H-24a, H-24b), 1.07 (m, H-17), 1.04 (m, H-15b), 0.99 (m, H-1b, H-22b), 0.98 (m, H-14),
0.96 (s, H-19), 0.90 (d, J ¼ 6.6Hz, H-21), 0.89 (m, H-9), 0.84 (d, J ¼ 6.6 Hz, H-26, H-27), 0.65