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Z.-Y. Zhu et al.
3033, 2871, 1728, 1602, 1492, 1315, 708; 1H
3.3.2. Ergosterol-3-O-(b-D-
glucopyranoside) (1a)
NMR (CDCl3) d (ppm): 8.15–7.25 (m, 20H,
ArH), 5.85–5.78 (m, 1H, H-40), 5.65–5.61
(m, 1H, H-20), 5.47 (dd, J ¼ 5.2, 1.6 Hz, 1H,
H-30), 5.37 (d, J ¼ 2.8 Hz, 1H, H-6), 5.23
(dd, J ¼ 12.4, 2.0 Hz, 1H, H-23), 5.13 (dd,
J ¼ 15.4, 8.8 Hz, 1H, H-22), 4.97 (d,
J ¼ 8.4 Hz, 1H, H-10), 4.71 (dd, J ¼ 11.2,
7.2 Hz, 1H, H-60), 4.47 (dd, J ¼ 11.2, 6.4 Hz,
1H, H-60), 4.37 (t, J ¼ 5.6 Hz, 1H, H-50),
3.74–3.63 (m, 1H, H-3), 1.28 (d, J ¼ 4.4 Hz,
3H, CH3-21), 1.07 (d, J ¼ 6.4 Hz, 3H,
CH3-27), 1.04 (s, 3H, CH3-19), 0.95 (d,
J ¼ 6.8 Hz, 3H, CH3-25), 0.86(t, J ¼ 6.8 Hz,
3H, CH3-28), 0.64 (s, 3H, CH3-18). HRE-
SIMS m/z: 997.4823 [M þ Na]þ (calcd for
C62H70O10Na, 997.4867).
Compound 3a (1 g, 1.03 mmol) was dis-
solved in MeOH–CH2Cl2 (1:1, 40 ml), and
then 40 mg NaOMe was added. After stirred
at rt for 3 h, the solution was neutralized with
ion-exchange resin (Hþ), and then filtered
and concentrated. The white residue was
purified by column chromatography
(CHCl3–MeOH 10:1 ! 6:1) to afford the
white solid 1a (0.57 g, 1.01 mol, 98.0%) with
the Rf 0.48 (CHCl3–MeOH, 6:1, V:V).
25
½aꢀD þ 12.2 (c ¼ 0.1, CH2Cl2); IR (KBr)
nmax cm21: 3385, 2956, 2871, 1457, 1369,
1
1027, 970; H NMR (DMSO-d6) d (ppm):
5.54 (d, J ¼ 4.8 Hz, 1H, H-6), 5.36–5.17 (m,
3H, H-7, 22, 23), 4.26 (d, J ¼ 7.8 Hz, 1H, H-
10), 3.61–3.56 (m, 1H, H-60), 3.45–3.43 (m,
2H, H-3, H-60), 3.16–3.03 (m, 3H, H-30, 40,
50), 2.40–2.91 (m, 1H, H-20), 1.02 (d,
J ¼ 6.6 Hz, 3H, CH3-21), 0.91 (t,
J ¼ 3.6 Hz, 3H, CH3-27), 0.89 (t,
J ¼ 6.6 Hz, 3H, CH3-25), 0.82 (t,
J ¼ 7.2 Hz, 3H, CH3-28), 0.62 (s, 3H, CH3-
19), 0.58 (s, 3H, CH3-18); 13C NMR
(DMSO-d6) d (ppm): 146.8 (C-8), 140.8
(C-5), 136.7 (C-22), 132.0 (C-23), 119.7
(C-6), 116.6 (C-7), 101.3 (C-10), 77.2 (C-50),
76.2 (C-30), 73.9 (C-20), 70.5 (C-40), 61.6
(C-60), 55.5 (C-17), 54.3 (C-14), 46.0 (C-9),
42.8 (C-13), 42.6 (C-24), 40.1 (C-20),
38.4 (C-12), 38.2 (C-4), 37.4 (C-1),
32.9 (C-25), 30.1 (C-2), 28.4 (C-10), 27.9
(C-16), 21.5 (C-15), 21.4 (C-26), 20.3
(C-11), 20.2 (C-21), 19.9 (C-27), 17.8
(C-28), 16.3 (C-19), 12.3 (C-18). HRESIMS
m/z: 581.3789 [M þ Na]þ (calcd for
C34H54O6Na, 581.3818).
3.3.4. Ergosterol-3-O-(b-D-
galactopyranoside) (1b)
The similar procedure for the preparation
of 1a was adopted, and thus 3b (1 g,
1.03 mmol) produced 1b (552.1 mg,
0.99 mol, 96.0%) as a white solid with
Rf 0.46 (CHCl3 –MeOH, 6:1, V:V).
25
½aꢀD þ 20.3 (c ¼ 0.1, CH2Cl2); IR (KBr)
n
max cm21: 3415, 2957, 2872, 1458, 1370,
1
1093, 1077, 802; H NMR (DMSO-d6) d
(ppm): 5.49 (d, J ¼ 5.4 Hz, 1H, H-6),
5.36–5.18 (m, 3H, H-7, 22, 23), 4.22 (d,
J ¼ 7.2 Hz, 1H, H-10), 3.50–3.57 (m, 1H,
H-40), 3.48–3.42 (m, 1H, H-60), 3.37–3.31
(m, 2H, H-60, H-3), 3.28–3.23 (m, 3H, H-
20, 30, 50), 1.02 (d, J ¼ 6.6 Hz, 3H, CH3-
21), 0.90 (t, J ¼ 3.6 Hz, 3H, CH3-27), 0.83
(t, J ¼ 4.2 Hz, 3H, CH3-25), 0.82 (t,
J ¼ 8.4 Hz, 3H, CH3-28), 0.61 (s, 3H,
CH3-19), 0.53 (s, 3H, CH3-18); 13C NMR
(DMSO-d6) d (ppm): 140.9 (C-8), 140.2
(C-5), 136.8 (C-23), 131.9 (C-22), 119.7
(C-6), 116.6 (C-7), 102.0 (C-10), 76.1 (C-
50), 75.5 (C-30), 73.9 (C-20), 71.1 (C-40),
68.6 (C-3), 60.9 (C-60), 55.5 (C-17), 54.4
(C-14), 46.0 (C-9), 42.8 (C-13), 42.5 (C-
24), 40.1 (C-20), 38.8 (C-12), 38.2 (C-4),
37.5 (C-1), 32.9 (C-25), 30.1 (C-2), 28.4
(C-10), 23.0 (C-16), 21.4 (C-15), 21.0 (C-
26), 20.2 (C-11), 20.1 (C-21), 19.9 (C-27),
3.3.3. Ergosterol-3-O-(2,3,4,6-tetra-O-
benzoyl-b-D-galactopyranoside) (3b)
The similar procedure for the preparation of
3a was adopted. Thus, ergosterol (0.22 g,
0.55 mmol) and 2b (0.37 g, 0.5 mmol)
produced 3b (453 mg, 0.465 mol, 93.0%) as
a white solid with Rf 0.41 (EtOAc–
25
petroleum ether, 1:4, V:V). ½aꢀD 2 9.5
(c ¼ 0.1, CH2Cl2); IR (KBr) nmax cm21
: