NATURAL PRODUCT RESEARCH
5
LH-20 gel CC eluted with MeOH to yield three subfractions (Frs. B9E3A–B9E3C), Fr.B9E3B
(2.3 g) was further separated by silica gel CC eluted with petroleum ether-acetone (100:25,
100:50, v/v) to give seven subfractions (Frs. B9E3B1–B9E3B7), and then Fr. B9E3B6 (463 mg)
was subjected to ODS silica gel CC eluted with MeOH–H2O (2:1, 3:1, 4:1, v/v) to yield eight
subfractions (Frs. B9E3B6A–B9E3B6H). Compound 4 (22 mg) was purified from Fr. B9E3B6F
(121 mg) by silica gel CC eluted with petroleum ether-acetone (100:25, v/v). Fr. B9F (10 g)
was subjected to silica gel CC eluted with CH2Cl2–MeOH (100:2, 100:3, 100:5, 100:10, v/v) to
afford four subfractions (Frs.B9F1–B9F4). Fr. B9F1 (5 g) further produced nine subfractions
(Frs. B9F1A–B9F1I) by silica gel CC eluted with petroleum ether-acetone (100:10, 100:20,
100:30, 100:50, v/v), Fr. B9F1E (1 g) was separated by Sephadex LH-20 gel CC eluted with
MeOH to yield compound 2 (32 mg). Fr. B9F3 (1.2 g) was separated by Sephadex LH-20 gel
CC eluted with MeOH to yield eight subfractions (Frs. B9F3A–B9F3H), Compound 5 (25 mg)
was purified from Fr. B9F3C (130 mg) by silica gel CC eluted with petroleum ether-acetone
(100:30, v/v). Fr. B9H (12 g) was subjected to silica gel CC eluted with petroleum ether-acetone
(100:20, 100:30, 100:40, v/v) to obtain nine subfractions (Frs. B9H1–B9H9). Fr. B9H6 (1.56 g)
was further separated by Sephadex LH-20 gel CC eluted with MeOH to yield six subfractions
(Frs. B9H6A–B9H6F), and then Fr. B9H6D (301 mg) was subjected to ODS silica gel CC eluted
with MeOH–H2O (80:20, v/v) to give compound 3 (40 mg). Fr. B9H7 (4 g) was subjected to
silica gel CC eluted with petroleum ether-EtOAc (1:3, 1:5, 1:7, v/v) to yield six subfractions
(Frs. B9H7A–B9H7F). Fr. B9H7E (1.5 g) was separated by Sephadex LH-20 gel CC eluted with
MeOH to yield compound 1 (175 mg).
3.3.1. 3-O-α-L-diginopyranosyl-(1→4)-β-D-digitoxopyranosyl -(1→4)-β-D-
cymaropyranosyl-(1→4)-β-D-thevetopyranosyl-14, 16:15, 20: 18, 20-triepoxy-14,
15-secopregn-4, 6, 8 (14)-triene (1)
White amorphous powder, ꢀ
20 + 41.0 (c 0.2, MeOH); IR(KBr) νmax 3451, 2973, 2935, 1677, 1634,
D
1453, 1382, 1308, 1258, 1166, 1064, 1023, 938, 869, 721 and 637 cm−1. HR-ESI-MS m/z:
1
943.4668 [M + Na]+ (calcd for C48H72 O17 Na, 943.4662). H NMR (400 MHz, C5D5 N)δ: 1.34
(m, Hα-1), 1.54 (m, Hβ-1), 2.24 (m, Hα-2), 1.94 (m, Hβ -2), 4.56 (brt, 7.8, H-3), 5.80 (brs, H-4), 5.90
(d, 9.7, H-6), 6.65 (d, 9.7, H-7), 2.13 (dd, 11.2, 5.8, H-9), 1.62 (o, Hβ-11), 1.21 (dd, 13.7, 11.2, Hα-
11), 1.99 (m, Hβ-12), 1.45 (m, Hα-12), 4.28 (d, 10.8, Hβ-15), 3.82 (dd, 4.3, 10.8, Hα-15), 4.82 (dd,
7.8, 4.3, H-16), 2.80 (d, 7.8, H-17), 4.02 (d, 8.8, Hβ-18), 4.07 (d, 8.8, Hα-18), 0.81 (s, H-19), 1.59
(s, H-21), β-D-the: 4.85 (d, 7.8, H-1′), 3.95 (m, H-2′), 3.73 (m, H-3′), 3.74 (m, H-4′), 3.70 (m, H-5′),
1.49 (d, 5.6, H-6′), 3.96 (s, 3′-OCH3), β-D-cym: 5.15 (d, 8.1, H-1″), 2.41 (m, Hβ-2″), 1.68 (m, Hα-2″),
3.94 (m, H-3″), 3.40 (m, H-4″), 4.22 (m, H-5″), 1.31 (d, 6.2, H-6″), 3.54 (s, 3″-OCH3), β-D-digt:
5.54 (d, 8.2, H-1‴), 2.46 (m, Hβ-2‴), 2.04 (m, Hα-2‴), 4.66 (m, H-3‴), 3.50 (dd, 9.9, 2.6, H-4‴),
4.32 (m, H-5‴), 1.42 (d, 6.2, H-6‴), α-L-dign: 5.21 (d, 3.2, H-1⁗), 2.41 (m, Hβ-2⁗), 2.11 (m, Hα-
2⁗), 3.86 (m, H-3⁗), 4.08 (m, H-4⁗), 4.31 (m, H-5⁗), 1.57 (d, 6.3, H-6⁗), 3.32 (s, 3⁗-OCH3).
13C NMR(100 MHz, C5D5 N) δ: 33.5 (C-1), 27.2 (C-2), 75.4 (C-3), 125.1 (C-4), 144.5 (C-5), 125.7
(C-6), 122.6 (C-7), 108.2 (C-8), 44.2 (C-9), 35.5 (C-10), 20.4 (C-11), 30.8 (C-12), 54.8 (C-13), 155.2
(C-14), 72.1 (C-15), 86.1 (C-16), 62.0 (C-17), 77.3 (C-18), 17.6 (C-19), 118.4 (C-20), 22.6 (C-21),
β-D-the: 103.3 (C-1′), 74.6 (C-2′), 85.8 (C-3′), 82.8 (C-4′), 71.7 (C-5′), 18.7 (C-6′), 60.5 (C-3′-OCH3),
β-D-cym: 99.6 (C-1″), 34.9 (C-2″), 77.4 (C-3″), 82.2 (C-4″), 69.3 (C-5″), 18.6 (C-6″), 57.3 (C-3″-
OCH3), β-D-digt: 98.9 (C-1‴), 39.1 (C-2‴), 67.68 (C-3‴), 83.2 (C-4‴), 68.8 (C-5‴), 18.5 (C-6‴),
α-L-dign: 101.2 (C-1⁗), 30.9 (C-2⁗), 75.8 (C-3⁗), 67.5 (C-4⁗⁗), 67.72 (C-5⁗), 17.74 (C-6⁗),
55.0 (C-3⁗ -OCH3).