6
T. YAN ET AL.
1
.76 (1 H, m, H-1b), 1.86 (1 H, m, H-2a), 2.13 (1 H, m, H-2b), 3.86 (1 H, m, H-3), 2.70
(1 H, m, H-4a), 2.79 (1 H, m, H-4b), 5.32 (1 H, br s, H-6),1.50 (1 H, m, H-7a), 1.89 (1 H,
m, H-7b), 1.68 (1 H, m, H-8), 0.92 (1 H, m, H-9),1.42 (1 H, m, H-11a), 1.49 (1 H, m, H-
1
1
0
2
2
1b), 1.11 (1 H, m, H-12a), 1.71 (1 H, m, H-12b), 1.07 (1 H, m, H-14), 1.50 (1 H, m, H-
5a), 2.04 (1 H, m, H-15b), 4.55 (1 H, m, H-16), 1.81 (1 H, dd, J ¼ 8.5, 6.5 Hz, H-17),
.83 (3 H, s, H-18), 1.03 (3 H, s, H-19), 1.95 (1 H, m, H-20), 1.14 (3 H, d, J ¼ 6.8 Hz, H-
1), 1.56–1.78 (2 H, m, H-23), 1.29 (1 H, m, H-24a), 1.57(1 H, m, H-24b), 1.57 (1 H, m, H-
5), 3.49 (1 H, t, J¼ 10.4 Hz, H-26a), 3.58 (1 H, br d, J¼ 10.4 Hz, H-26b), 0.68 (3 H, d,
J¼ 5.6 Hz, H-27), 4.91 (1 H, d, J¼ 7.6 Hz, H-1’), 4.22 (1 H, dd, J ¼ 9.0, 7.6 Hz, H-2’), 4.18
(
1 H, t, J¼ 9.0 Hz, H-3’), 4.09 (1 H, t, J¼ 9.2 Hz, H-4’), 3.82 (1 H, m, H-5’), 4.57 (1 H, m, H-
’a), 4.71 (1 H, br d, J¼ 11.8 Hz, H-6’b), 6.35 (1H, s, H-1”), 4.80 (1 H, br s, H-2”), 4.61
1 H, dd, J¼ 9.4, 3.3 Hz, H-3”), 4.35 (1 H, t, J¼ 9.4 Hz, H-4”), 4.92 (1 H, m, H-5”), 1.75 (3 H,
d, J¼ 6.1 Hz, H-6”), 5.52 (1 H, s, H-1’“), 4.63 (1 H, br s, H-2’“), 4.49 (1 H, dd, J¼ 9.3,
.0 Hz, H-3’“), 4.32 (1 H, t, J¼ 9.3 Hz, H-4’“), 4.82 (1 H, m, H-5’“), 1.62 (3 H, d, J¼ 6.2 Hz,
H-6’“), 2.34 (2 H, t, J¼ 7.5 Hz, H-2’’“), 1.62 (2 H, m, H-3’’“), 2.10 (2 H, m, H-8’’“/H-14’’“),
.46-5.51 (4 H, m, H-9’’“/H-10’’“/H-12’’“/H-13’’“), 2.92 (2 H, t, J¼ 5.8 Hz, H-11’’“), 1.26 (2 H,
m, H-16’“’), 1.25 (2 H, m, H-17’“’), 0.85 (2 H, t, J¼ 6.5 Hz, H-18’“’), 1.18-1.37(2H, m, other
6
(
3
5
1
3
CH ). C-NMR (100 MHz, pyridine-d ) d 37.6 (t, C-1), 30.2 (t, C-2), 78.8 (d, C-3), 39.1
2
5
C
(t,C-4), 140.9 (s,C-5), 121.8 (d,C-6), 32.4 (t,C-7), 31.9 (d,C-8), 50.4 (d,C-9), 37.2 (s,C-10), 21.2
(t,C-11), 39.9 (t,C-12), 40.5 (s,C-13), 56.7 (d,C-14), 32.3 (t,C-15), 81.1 (d,C-16), 63.0 (d,C-
17),16.4 (q,C-18),19.4 (q,C-19),42.0 (d,C-20),15.1 (q,C-21), 109.3 (s,C-22), 31.7(t,C-23),
29.3(t,C-24), 30.6 (d,C-25), 66.9 (t,C-26), 17.4 (q,C-27), 100.6 (d,C-1’), 77.6 (d,C-2 ’), 77.7
(
7
(
8
d,C-3’),79.6 (d,C-4’), 73.6 (d,C-5’), 63.3 (t,C-6), 102.2 (d,C-1”), 72.5 (d,C-2”), 72.8 (d,C-3”),
4.1 (d,C-4”), 69.6 (d,C-5”), 18.7 (q,C-6”), 103.2 (d,C-1’“), 72.4 (d,C-2’“), 72.7 (d,C-3’“), 73.7
d,C-4’“), 70.8 (d,C-5’“), 18.5 (q,C-6’“), 173.3 (s,C-1’“’), 34.4 (t,C-2’“’), 25.3 (t,C-3’“’),27.6 (t, C-
’’“/C-14’’“), 128.5,128.5,130.3,130.5 (d, C-9’“’, C-10’“’, C-12’“’,C-13’“’), 26.1 (t, C-11’“’), 32.2
(
t,C-16’“’), 23.0 (t,C-17’“’), 14.3 (q,C-18’“’), 29.4–30.1 (t, other CH ).
2
20
Trilliumoside: light yellow amorphous powder; [a]
– 79.0 (c 0.30, MeOH); HR-ESI-MS
D
þ
data m/z 613.3348 [M þ Na] (calc. for C H O 613.3347); UV (MeOH) k
250 nm; IR
33
50
9
max
ꢀ
1 1
(KBr) ꢀ
3423, 2925, 2853, 1717, 1631, 1463, 1383, 1264, 1169, 1043, 616 cm . H-NMR
max
(
600MHz, MeOH) d 1.10 (1 H, m, H-1a), 1.89 (1 H, m, H-1b), 1.80 (1 H, m, H-2a), 1.99 (1 H,
H
m, H-2b), 3.40 (1H, m, H-3), 2.22 (1 H, m, H-4a), 2.25 (1 H, m, H-4b), 5.36 (1 H, br d,
J ¼ 4.5Hz, H-6), 1.65 (1 H, m, H-7a), 1.99 (1 H, m, H-7b), 1.80 (1 H, m, H-8), 1.15 (1 H, m, H-9),
1
.70-1.87 (2 H, m, H-11), 1.75 (1 H, m, H-12a), 2.35 (1 H, m, H-12b), 1.60 (1H, m, H-14), 2.08
(
1H, m, H-15a), 2.17 (1 H, m, H-15b), 1.13(3 H, s, CH -18), 1.08(3 H, s, CH -19), 1.95 (3 H, s,
3 3
CH -21), 2.58 (2H, t, J ¼ 7.4 Hz, H-23), 1.50 (1 H, m, H-24a), 1.78(1 H, m, H-24b), 1.80 (1 H, m,
3
H-25), 3.39 (1 H, dd, J ¼ 9.5, 6.1 Hz, H-26a), 3.73 (1H, dd, J ¼ 9.5, 6.1 Hz, H-26b), 0.94 (3H, d,
J ¼ 6.4 Hz, CH -27), 4.23 (1H, d, J ¼ 7.8 Hz, H-1’), 3.17 (1 H, dd, J ¼ 9.0, 7.8, H-2’), 3.32 (1 H, m,
3
H-3’), 3.26 (1 H, m, H-4’), 3.25 (1 H, m, H-5’), 3.65 (1 H, J ¼ 11.5, 5.2 Hz, H-6’a), 3.85 (1 H, dd,
1
3
J ¼ 11.5,1.6 Hz, H-6’b). C-NMR (150 MHz, MeOH) d 38.2 (t, C-1), 32.2 (t,C-2), 72.3 (d,C-3),
C
4
2
1
3.0 (t,C-4), 142.5 (s,C-5), 121.9 (d,C-6), 32.5 (t,C-7), 32.0 (d,C-8), 51.2 (d,C-9), 37.8 (s,C-10),
1.9 (t,C-11), 37.3 (t,C-12), 44.6 (s,C-13), 52.1 (d,C-14), 38.6 (t,C-15), 207.9 (s,C-16), 143.9 (s,C-
8), 17.1 (q,C-18), 19.8 (q,C-19), 146.9 (s,C-20), 15.9 (q,C-21), 213.9 (s,C-22), 39.3 (t,C-23), 28.3
(t,C-24), 34.0 (d,C-25), 75.8 (t,C-26), 17.4 (q,C-27), 104.6 (d,C-1’), 75.2 (d,C-2’), 78.2 (d,C-3’),
71.7 (d,C-4’), 77.9 (d,C-5’), 62.8 (t,C-6’).