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J.-l. Zhang et al. / Steroids 74 (2009) 424–434
(3H, s, 19ꢀ-CH3), 0.92 (3H, d, 21ꢀ-CH3), 3.59 (1H, m, 3ꢀ-CH), 3.67
(3H, s, –OCH3), 4.03 (1H, m, 6ꢀ-CH).
1729, 1451, 1379, 1252, 1169, 1102, 1021, 988, 875, 837, 773. 1H NMR
(400 MHz, CDCl3), ı: 0.67 (3H, s, 18ꢀ-CH3), 0.92 (3H, s, 19ꢀ-CH3),
0.94 (3H, d, 21ꢀ-CH3), 3.51 (1H, m, 3ꢀ-CH), 3.61 (1H, m, 7ꢀ␣-CH),
3.67 (3H, s, –OCH3).
2.2.4.3. 3˛-tert-butyldimethylsilyloxy-6˛-hydroxy-5ˇ-cholan-24-
oic acid (18). This compound was synthesized with the same
procedure as described for 3, with different reactants. The title
compound 18 was in the form of colorless crystals: yield, 4.86 g
(96%); m.p., 206–208 ◦C. IR (cm−1): 3395, 2942, 2858, 1730, 1467,
1444, 1392, 1252, 1173, 1096, 1029, 963, 873, 837, 774. 1H NMR
(400 MHz, CDCl3), ı: 0.64 (3H, s, 18ꢀ-CH3), 0.90 (3H, s, 19ꢀ-CH3),
0.93 (3H, d, 21ꢀ-CH3), 3.59 (1H, m, 3ꢀ-CH), 4.05 (1H, m, 6ꢀ-CH).
2.2.3.9. 3˛-tert-butyldimethylsilyloxy-7ˇ-hydroxy-5ˇ-cholan-24-
oic acid (13). This compound was synthesized with the same
procedure as described for 3, with different reactants. The title
compound 13 was in the form of colorless crystals: yield, 4.76 g
(94%); m.p., 218–221 ◦C. IR (cm−1): 3546, 3384, 2931, 2859, 1702,
1467, 1381, 1255, 1099, 1018, 952, 873, 836, 775. 1H NMR (400 MHz,
CDCl3), ı: 0.67 (3H, s, 18ꢀ-CH3), 0.92 (3H, s, 19ꢀ-CH3), 0.95 (3H, d,
21ꢀ-CH3), 3.52 (1H, m, 3ꢀ-CH), 3.62 (1H, m, 7ꢀ␣-CH).
2.2.4.4. 5˛,14˛-cevanin-6-O-20ˇ-hydroxy-3ˇ-yl-3˛-tert-
butyldimethylsilyloxy-6˛-hydroxy-5ˇ-cholan-24-oate
(19). This
2.2.3.10. 5˛,14˛-cevanin-6-O-20ˇ-hydroxy-3ˇ-yl-3˛-tert-
compound was synthesized with the same procedure as described
for 4, with different reactants. The title compound 19 was found as
a colorless solid: yield: 2.83 g (51.5%); m.p., 179–182 ◦C. IR (cm−1):
3528, 3311, 2931, 2856, 2757, 1699, 1673, 1658, 1453, 1381, 1252,
1168, 1087, 1004, 986, 875, 837, 774. 1H NMR (400 MHz, CDCl3), ı:
0.64 (3H, s, 18ꢀ-CH3), 0.90 (3H, s, 19ꢀ-CH3), 0.93 (3H, d, 21ꢀ-CH3),
3.58 (1H, m, 3ꢀ-CH), 4.05 (1H, m, 6ꢀ-CH), 4.68 (1H, m, 3␣-CH),
0.80 (3H, s, 19-CH3), 1.04 (3H, s, 21-CH3), 1.09 (3H, d, 27-CH3).
butyldimethylsilyloxy-7ˇ-hydroxy-5ˇ-cholan-24-oate
(14). This
compound was synthesized with the same procedure as described
for 4, with different reactants. The title compound 14 was found as
a colorless solid: yield: 3.06 g (55.6%); m.p., 160–162 ◦C. IR (cm−1):
3456, 2932, 2857, 2775, 1734, 1713, 1690, 1466, 1451, 1379, 1254,
1233, 1170, 1079, 956, 872, 836, 775. 1H NMR (400 MHz, CDCl3), ı:
0.67 (3H, s, 18ꢀ-CH3), 0.92 (3H, s, 19ꢀ-CH3), 0.93 (3H, d, 21ꢀ-CH3),
3.51 (1H, m, 3ꢀ-CH), 3.60 (1H, m, 7ꢀ ␣-CH), 4.69 (1H, m, 3␣-CH),
0.79 (3H, s, 19-CH3), 1.03 (3H, s, 21-CH3), 1.09 (3H, d, 27-CH3).
2.2.4.5. 5˛,14˛-cevanin-6-O-20ˇ-hydroxy-3ˇ-yl-3˛,6˛-dihydroxy-
5ˇ-cholan-24-oate (20). This compound was synthesized with the
same procedure as described for 5, with different reactants. The
title compound 20 was found as a colorless amorphous solid: yield:
2.10 g (97%); m.p., 121.5–123.6 ◦C. [˛]D20 = −52.5 (c 0.001, CHCl3). IR
(cm−1): 3381, 2935, 2870, 2777, 1712, 1454, 1380, 1243, 1167, 1038,
957. EI-MS m/z: 804 ([M + H]+, 12.84%), 803 (M+, 3.36%). HRESIMS
calculated for C51H82NO6 [M + H]+:804.6137; found: 804.6131. Its
analysis led to the molecular formula C51H81NO6, supported by the
13C NMR, H–H COSY, HSQC and DEPT data. The 1H NMR spectrum
(Table 1) showed a set of downfield resonances at ı 4.67 (1H, m,
3␣-CH), 4.06 (1H, m, 6ꢀ-CH), 3.62 (1H, m, 3ꢀ-CH) and a set of
typical upfield resonances at ı 1.09 (3H, d, 27-CH3), 1.04 (3H, s,
21-CH3), 0.93 (3H, d, 21ꢀ-CH3), 0.90 (3H, s, 19ꢀ-CH3), 0.79 (3H, s,
19-CH3), 0.64 (3H, s, 18ꢀ-CH3). The 13C NMR spectrum (Table 3)
showed a set of typical resonances at ı 210.4 (C-6), 173.8 (C-24ꢀ),
72.8 (C-3), 71.6 (C-3ꢀ), 70.9 (C-20), 70.6 (C-22), 68.1 (C-6ꢀ), 62.1
(C-26), 61.8 (C-18), 56.4 (C-9), 56.2 (C-5).
2.2.3.11. 5˛,14˛-cevanin-6-O-20ˇ-hydroxy-3ˇ-yl-3˛,7ˇ-dihydroxy-
5ˇ-cholan-24-oate (15). This compound was synthesized with the
same procedure as described for 5, with different reactants. The
title compound 15 was found as a colorless amorphous solid: yield:
2.06 g (95%); m.p., 126.5–128.5 ◦C. [˛]D20 = 34.5 (c 0.001, CHCl3).
IR (cm−1): 3411, 2933, 2859, 1709, 1452, 1383, 1255, 1237, 1171,
1080, 1053, 959. EI-MS m/z: 804 ([M + H]+, 4.26%), 803 (M+, 2.26%).
HRESIMS calculated for
804.6124. Its analysis led to the molecular formula C51H81NO6,
supported by the 13C NMR, H–H COSY, HSQC and DEPT data. The 1
C
51H82NO6 [M + H]+:804.6137; found:
H
ı 4.68 (1H, m, 3␣-CH), 3.68 (1H, m, 7ꢀ␣-CH), 3.58 (1H, m, 3ꢀ-CH)
and a set of typical upfield resonances at ı 1.07 (3H, d, 27-CH3),
1.03 (3H, s, 21-CH3), 0.96 (3H, d, 21ꢀ-CH3), 0.88 (3H, s, 19ꢀ-CH3),
0.79 (3H, s, 19-CH3), 0.68 (3H, s, 18ꢀ-CH3). The 13C NMR spectrum
(Table 3) showed a set of typical resonances at ı 210.2 (C-6), 173.8
(C-24ꢀ), 72.8 (C-3), 71.5 (C-3ꢀ), 71.5 (C-20), 71.4 (C-22), 71.4 (C-7ꢀ),
62.3 (C-26), 61.1 (C-18), 56.5 (C-9), 55.8 (C-5).
2.2.5. Deoxycholic acid–verticinone ester (DCA-Ver)
2.2.4. Hyodeoxycholic acid–verticinone ester (HDCA-Ver)
The synthetic route for the DCA-Ver is shown in Scheme 1. The
IH NMR chemical shifts of DCA-Ver are listed in Table 1 and the IH
NMR chemical shifts of intermediate products are listed in Table 2.
The 13C NMR chemical shifts of DCA-Ver are listed in Table 3.
The synthetic route for the HDCA-Ver is shown in Scheme 1. The
IH NMR chemical shifts of HDCA-Ver are listed in Table 1 and the IH
NMR chemical shifts of intermediate products are listed in Table 2.
The 13C NMR chemical shifts of HDCA-Ver are listed in Table 3.
2.2.5.1. Methyl 3˛,12˛-dihydroxy-5ˇ-cholan-24-oate (21). This
compound was synthesized with the same procedure as described
for 1, with different reactants. The title compound 21 was in the
form of colorless crystals: yield, 20.6 g (84.5%); m.p., 148–150 ◦C.
IR (cm−1): 3630, 3511, 3332, 2943, 2867, 1744, 1449, 1372, 1249,
1196, 1164, 1039, 1017, 973. 1H NMR (400 MHz, CDCl3), ı: 0.67 (3H,
s, 18ꢀ-CH3), 0.90 (3H, s, 19ꢀ-CH3), 0.96 (3H, d, 21ꢀ-CH3), 3.61 (1H, m,
3ꢀ-CH), 3.67 (3H, s, –OCH3), 3.98 (1H, m, 12ꢀ-CH).
2.2.4.1. Methyl 3˛,6˛-dihydroxy-5ˇ-cholan-24-oate (16). This com-
pound was synthesized with the same procedure as described for
1, with different reactants. The title compound 16 was in the form
of colorless crystals: yield, 20.34 g (83.5%); m.p., 122–124 ◦C. IR
(cm−1): 3392, 2938, 2866, 1742, 1452, 1377, 1255, 1168, 1039, 957.
1H NMR (400 MHz, CDCl3), ı: 0.64 (3H, s, 18ꢀ-CH3), 0.90 (3H, s,
19ꢀ-CH3), 0.93 (3H, d, 21ꢀ-CH3), 3.62 (1H, m, 3ꢀ-CH), 3.67 (3H, s,
–OCH3), 4.05 (1H, m, 6ꢀ-CH).
2.2.4.2. Methyl
3˛-tert-butyldimethylsilyloxy-6˛-hydroxy-5ˇ-
2.2.5.2. Methyl
3˛-tert-butyldimethylsilyloxy-12˛-hydroxy-5ˇ-
cholan-24-oate (17). This compound was synthesized with the
same procedure as described for 2, with different reactants. The
title compound 17 was in the form of colorless amorphous solids:
yield, 5.62 g (72.1%); m.p., 151–153 ◦C. IR (cm−1): 3602, 3418, 2941,
2858, 1733, 1467, 1440, 1377, 1311, 1251, 1168, 1073, 1033, 988, 871,
837, 775. 1H NMR (400 MHz, CDCl3), ı: 0.63 (3H, s, 18ꢀ-CH3), 0.90
cholan-24-oate (22). This compound was synthesized with the
same procedure as described for 2, with different reactants. The
title compound 22 was in the form of colorless amorphous solids:
yield, 5.73 g (73.5%); m.p., 165–167 ◦C. IR (cm−1): 3623, 3453, 2940,
2862, 1737, 1465, 1444, 1377, 1252, 1211, 1175, 1100, 1030, 949,
876, 840, 774. 1H NMR (400 MHz, CDCl3), ı: 0.67 (3H, s, 18ꢀ-CH3),