S. Kawakami et al. / Phytochemistry 72 (2011) 147–153
151
ddd, J = 9, 6, 3 Hz, H-50), 3.37 (1H, dd, J = 9, 9 Hz, H-30), 3.33 (1H, m,
H-40), 3.18 (1H, dd, J = 9, 8 Hz, H-20), 1.75 (2H, overlapped, H-4a and
5), 1.67 (1H, dd, J = 12, 12 Hz, H-2a), 1.51 (1H, ddd, J = 12, 4, 2 Hz,
H-2b), 1.44 (1H, ddd, J = 12, 12, 12 Hz, H-4b), 1.20 (3H, d, J = 6 Hz,
H3-10), 0.88 (3H, s, H3-11), 0.86 (3H, s, H3-12), 0.72 (3H, d,
J = 6 Hz, H3-13); for 13C NMR (CD3OD, 100 MHz) spectroscopic
data, see Table 1; HR-ESI-TOF-MS (positive-ion mode) m/z:
619.2710 [MNa] (calcd for C30H44O12Na, 619.2730).
J = 6 Hz, H3-10), 0.95 (3H, s, H3-11), 0.87 (3H, s, H3-12), 0.79 (3H,
d, J = 6 Hz, H3-13); for 13C NMR (CD3OD, 100 MHz) spectroscopic
data, see Table 1; HR-ESI-TOF–MS (positive-ion mode) m/z:
751.3124 [MNa] (calcd for C35H52O16Na, 751.3153).
4.4.6. Crotonionoside F (6)
Amorphous powder; ½a D23
ꢁ55.8 (c 0.53, MeOH); IR kmax
ꢀ
(film) cmꢁ1: 3366, 2964, 1647, 1457, 1367; 1H NMR (CD3OD,
400 MHz) d: 5.45 (1H, dd, J = 15, 6 Hz, H-8), 5.30 (1H, ddd, J = 15,
10, 2 Hz, H-7), 5.38 (1H, d, J = 1 Hz, H-100), 4.42 (1H, d, J = 8 Hz,
H-10), 4.22 (1H, dqd, J = 6, 6, 2 Hz, H-9), 4.05 (1H, d, J = 10 Hz,
H-400a), 3.94 (1H, d, J = 1 Hz, H-200), 3.86 (1H, dddd, J = 12, 12, 4,
4 Hz, H-3), 3.84 (1H, dd, J = 12, 2 Hz, H-60a), 3.73 (1H, d, J = 10 Hz,
H-400b), 3.65 (1H, dd, J = 12, 5 Hz, H-60b), 3.63 (1H, d, J = 11 Hz,
H-500a), 3.60 (1H, d, J = 11 Hz, H-500b), 3.46 (1H, dd, J = 9, 9 Hz,
H-30), 3.32 (1H, m, H-20), 3.26 (1H, m, H-40), 3.23 (1H, ddd, J = 9,
5, 2 Hz, H-50), 2.11 (1H, dddd, J = 12, 4, 4, 2 Hz, H-4a), 1.84 (1H,
ddd, J = 12, 4, 2 Hz, H-2a), 1.51 (1H, m, H-5), 1.32 (1H, dd, J = 10,
10 Hz, H-6), 1.22 (3H, d, J = 6 Hz, H-10), 1.15 (1H, dd, J = 12,
12 Hz, H-2b), 1.01 (1H, ddd, J = 12, 12, 12 Hz, H-4b), 0.91 (3H, s,
H3-12), 0.86 (3H, s, H3-11), 0.83 (3H, d, J = 7 Hz, H3-13); for 13C
NMR (CD3OD, 100 MHz) spectroscopic data, see Table 1; HR-ESI-
TOF–MS (positive-ion mode) m/z: 529.2635 [MNa] (calcd for
4.4.3. Crotonionoside C (3)
Amorphous powder;
½
a 2D4
ꢀ
ꢁ69.9 (c 0.62, MeOH); IR kmax
(film) cmꢁ1: 3367, 2968, 1648, 1457, 1367; 1H NMR (CD3OD,
400 MHz) d: 5.73 (1H, dd, J = 15, 6 Hz, H-8), 5.55 (1H, dd, J = 15,
1 Hz, H-7), 5.39 (1H, d, J = 1 Hz, H-100), 4.42 (1H, d, J = 7 Hz, H-10),
4.29 (1H, dqd, J = 6, 6, 1 Hz, H-9), 4.08 (1H, d, J = 10 Hz, H-400a),
3.94 (1H, d, J = 1 Hz, H-200), 3.93 (1H, dddd, J = 12, 12, 4, 4 Hz, H-
3), 5.39 (1H, d, J = 1 Hz, H-100), 3.85 (1H, dd, J = 12, 2 Hz, H-60a),
3.72 (1H, d, J = 10 Hz, H-400b), 3.65 (1H, dd, J = 12, 5 Hz, H-60b),
3.64 (2H, s, H-500), 3.47 (1H, dd, J = 9, 9 Hz, H-30), 3.32 (1H, m,
H-20), 3.28 (1H, dd, J = 9, 9 Hz, H-40), 3.24 (1H, ddd, J = 9, 5, 2 Hz,
H-50), 1.93 (1H, dqd, J = 12, 7, 4 Hz, H-5), 1.83 (1H, dddd, J = 12, 4,
4, 2 Hz, H-4 eq), 1.68 (1H, dd, J = 12, 12 Hz, H-2ax), 1.56 (1H, ddd,
J = 12, 4, 2 Hz, H-2 eq), 1.49 (1H, ddd, J = 12, 12, 12 Hz, H-4ax),
1.24 (3H, d, J = 6 Hz, H3-10), 0.98 (3H, s, H3-11), 0.91 (3H, s, H3-
12), 0.81 (3H, d, J = 7 Hz, H3-13); for 13C NMR (CD3OD, 100 MHz)
spectroscopic data, see Table 1; HR-ESI-TOF–MS (positive-ion
mode) m/z: 545.2546 [MNa] (calcd for C24H42O12Na, 545.2568).
C24H42O11Na, 529.2619).
4.4.7. Crotonionoside G (7)
Amorphous powder; ½a D23
ꢁ63.6 (c 0.11, MeOH); IR kmax
ꢀ
(film) cmꢁ1: 3343, 2926, 2856, 1712, 1630, 1599, 1515, 1455,
4.4.4. Crotonionoside D (4)
1261 ; UV mmax (MeOH) nm (log e
): 323 (3.98), 214 (4.11); 1H
Amorphous powder;
(film) cmꢁ1: 3395, 2967, 2879, 1701, 1607, 1455, 1368; UV mmax
(MeOH) nm (log
): 258 (4.04), 209 (4.04); 1H NMR (CD3OD,
½
a 2D4
ꢀ
ꢁ38.5 (c 0.13, MeOH); IR kmax
NMR (CD3OD, 400 MHz) d: 7.62 (1H, d, J = 16 Hz, H-700), 7.16 (1H,
d, J = 2 Hz, H-200), 7.04 (1H, dd, J = 8, 2 Hz, H-600), 6.81 (1H, d,
J = 8 Hz, H-500), 6.35 (1H, d, J = 16 Hz, H-800), 5.97 (1H, dd, J = 16,
1 Hz, H-7), 5.46 (1H, dd, J = 16, 6 Hz, H-8), 4.50 (1H, d, J = 8 Hz,
H-10), 4.49 (1H, dd, J = 12, 6 Hz, H-60a), 4.48 (1H, dd, J = 12, 3 Hz,
H-60b), 4.27 (1H, dqd, J = 6, 6, 1 Hz, H-9), 4.04 (1H, br d, J = 4 Hz,
H-4), 3.91 (1H, ddd, J = 13, 4, 4 Hz, H-3), 3.89 (3H, s, 300-OMe),
3.57 (1H, ddd, J = 9, 6, 3 Hz, H-50), 3.41 (1H, dd, J = 9, 9 Hz, H-30),
3.34 (1H, m, H-40), 3.26 (1H, dd, J = 9, 8 Hz, H-20), 1.87 (1H, dd,
J = 13, 13 Hz, H-2a), 1.82 (1H, d, J = 1 Hz, H3-13), 1.58 (1H, ddd,
J = 13, 4, 1 Hz, H-2b), 1.23 (3H, d, J = 6 Hz, H3-10), 1.03 (3H, s,
H3-11), 0.99 (3H, s, H3-12); for 13C NMR (CD3OD, 100 MHz) spec-
troscopic data, see Table 1; HR-ESI-TOF–MS (positive-ion mode)
m/z: 587.2444 [MNa] (calcd for C29H40O11Na, 587.2468).
e
400 MHz) d: 7.94 (2H, d, J = 9 Hz, H-2000 and 6000), 6.84 (2H, d,
J = 9 Hz, H-3000 and 5000), 5.68 (1H, dd, J = 16, 6 Hz, H-8), 5.50 (1H,
dd, J = 16, 1 Hz, H-7), 5.44 (1H, d, J = 1 Hz, H-100), 4.43 (1H, d,
J = 11 Hz, H-500a), 4.42 (1H, d, J = 8 Hz, H-10), 4.32 (1H, d, J = 11 Hz,
H-500b), 4.26 (1H, dqd, J = 6, 6, 1 Hz, H-9), 4.24 (1H, d, J = 10 Hz,
H-400a), 4.05 (1H, d, J = 10 Hz, H-200), 3.85 (1H, dddd, J = 12, 12, 4,
4 Hz, H-3), 3.85 (1H, dd, J = 12, 2 Hz, H-60a), 3.84 (1H, d, J = 10 Hz,
H-400b), 3.65 (1H, dd, J = 12, 5 Hz, H-60b), 3.49 (1H, dd, J = 9, 9 Hz,
H-30), 3.35 (1H, dd, J = 9, 8 Hz, H-20), 3.28 (1H, m, H-40), 3.25 (1H,
m, H-50), 1.86 (1H, dqd, J = 12, 7, 4 Hz, H-5), 1.83 (1H, m, H-4a),
1.65 (1H, dd, J = 12, 12 Hz, H-2a), 1.48 (1H, ddd, J = 12, 4, 2 Hz,
H-2b), 1.46 (1H, ddd, J = 12, 12, 12 Hz, H-4b), 1.22 (3H, d, J = 6 Hz,
H3-10), 0.88 (3H, s, H3-11), 0.78 (3H, s, H3-12), 0.77 (3H, d,
J = 7 Hz, H3-13); for 13C NMR (CD3OD, 100 MHz) spectroscopic
data, see Table 1; HR-ESI-TOF–MS (positive-ion mode) m/z:
665.2782 [MNa] (calcd for C31H46O14Na, 665.2779).
4.4.8. Mild alkaline hydrolysis of crotonionosides A (1)–B (2), D (4)–E
(5), and G (7)
To a solution of crotonionoside A (1) (5.9 mg) in MeOH (450
ll)
was added 1 M CH3ONa (50 l), followed by standing at 20 °C for
l
4.4.5. Crotonionoside E (5)
4 h. The reaction mixture was neutralized with Amberlite IR-
120B (H+) and then evaporated to dryness. The residue was
partitioned with CHCl3 (2 ml)-H2O (2 ml) to afford a megastigmane
glycoside (1a = 8) (2.3 mg) from the H2O-soluble fraction and
methyl ferulate (1b) (1.0 mg) from the CHCl3-soluble fraction.
In a similar manner to as for 1, crotonionoside B (2) (2.2 mg)
gave a megastismane glycoside (2a = 8) (1.0 mg) and methyl sina-
pate (2b) (0.4 mg).
Amorphous powder;
(film) cmꢁ1: 3395, 2966, 2881, 1702, 1631, 1516, 1458, 1285; UV
mmax (MeOH) nm (log
): 327 (4.08) 239 (4.05), 225 (4.03); 1H
½
a 2D2
ꢀ
ꢁ50.6 (c 0.18, MeOH); IR kmax
e
NMR (CD3OD, 400 MHz) d: 7.67 (1H, d, J = 16 Hz, H-7000), 6.92 (2H,
s, H-2000 and 6000), 6.43 (1H, d, J = 16 Hz, H-8000), 5.68 (1H, dd, J = 15,
6 Hz, H-8), 5.51 (1H, dd, J = 15, 1 Hz, H-7), 5.44 (1H, d, J = 1 Hz,
H-100), 4.43 (1H, d, J = 8 Hz, H-10), 4.38 (1H, d, J = 11 Hz, H-500a),
4.27 (1H, d, J = 11 Hz, H-500b), 4.26 (1H, dqd, J = 6, 6, 1 Hz, H-9),
4.21 (1H, d, J = 10 Hz, H-400a), 3.97 (1H, d, J = 1 Hz, H-200), 3.92
(1H, dddd, J = 12, 12, 4, 4 Hz, H-3), 3.88 (6H, s, 3000 and 5000-OMe),
3.85 (1H, overlapped, H-60a), 3.82 (1H, d, J = 10 Hz, H-400b), 3.65
(1H, dd, J = 12, 5 Hz, H-60b), 3.49 (1H, dd, J = 9, 9 Hz, H-30), 3.35
(1H, dd, J = 9, 8 Hz, H-20), 3.28 (1H, m, H-40), 3.23 (1H, ddd, J = 9,
5, 2 Hz, H-50), 1.90 (1H, dqd, J = 12, 6, 4 Hz, H-5), 1.83 (1H, m,
H-4a), 1.69 (1H, dd, J = 12, 12 Hz, H-2a), 1.54 (1H, ddd, J = 12, 4,
2 Hz, H-2b), 1.48 (1H, ddd, J = 12, 12, 12 Hz, H-4b), 1.21 (3H, d,
Crotonionoside D (4) (2.6 mg) and E (5) (1.6 mg) gave 3 (1.7 mg)
and a methyl p-hydroxybenzoate (4b) (0.1 mg), and 3 (0.9 mg) and
methyl sinapate (2b) (0.4 mg), respectively.
Crotonionoside G (7) (1.7 mg) gave a megastismane glycoside
(7a) (1.3 mg) and a methyl ferulate (1b) (0.2 mg).
Plucheoside B (7a); amorphous powder; ½a D27
ꢀ
45.6 (c 0.09,
MeOH); NMR data were essentially the same as those reported
(Otsuka et al., 1995b); HR-ESI TOF–MS (positive-ion mode) m/z:
411.2000 [MNa] (calcd for C19H32O8Na, 411.1989).