N. Tsutsui et al. / European Journal of Medicinal Chemistry 121 (2016) 250e271
267
J ¼ 8.3, 6.0, 3.7 Hz,1H, H-5), 3.69 (dd, J ¼ 10.6, 6.4 Hz,1H, H-1a), 3.72
calcd for C37H66O15Na [M þ Na]þ: 773.4299; found: 773.4310.
(dd, J ¼ 8.5, 0.9 Hz, 1H, H-3), 3.75 (dd, J ¼ 8.3, 0.9 Hz, 1H, H-4), 3.78
(ddd, J ¼ 8.5, 6.4, 2.6 Hz, 1H, H-2), 3.79 (dd, J ¼ 11.3, 3.7 Hz, 1H, H-
6b), 3.83 (ddd, J ¼ 9.8, 4.6, 2.3 Hz,1H, H-50), 4.13 (dd, J ¼ 10.6, 2.6 Hz,
1H, H-1b), 4.14 (dd, J ¼ 12.3, 2.3 Hz, 1H, H-60a), 4.27 (dd, J ¼ 12.4,
4.6 Hz, 1H, H-60b), 4.92 (d, J ¼ 0.7 Hz, 1H, H-10), 5.17 (dd, J ¼ 10.1,
3.2 Hz,1H, H-30), 5.28 (dd, J ¼ 10.1, 9.8 Hz,1H, H-40), 5.51 (dd, J ¼ 3.2,
25
3.1.26.5. Compound 2n. Colorless amorphous. [
a]
ꢁ 27.8 (c 0.98,
D
CHCl3). IR (neat) cmꢁ1: 3383, 1748, 1416, 1377, 1246, 1169, 1103,
1069. 1H NMR (800 MHz, CD3OD)
: 0.896 (t, J ¼ 7.1 Hz, 6H, acyl
d
CH3), 0.899/0.92 (each t, J ¼ 6.9 Hz, 3H, acyl CH3), 1.24e1.43 (m,
22H, acyl CH2), 1.51e1.59 (m, 4H, COCH2CH2), 1.63e1.70 (m, 4H,
COCH2CH2), 2.19/2.21/2.27/2.31 (each dt, J ¼ 15.8, 7.3 Hz, 1H,
COCH2), 2.34/2.37 (each dt, J ¼ 15.8, 7.6 Hz, 1H, COCH2), 2.39/2.47
(each dt, J ¼ 15.4, 7.3 Hz,1H, COCH2), 3.61 (dd, J ¼ 11.3, 6.2 Hz,1H, H-
6a), 3.66 (ddd, J ¼ 8.3, 6.2, 3.7 Hz, 1H, H-5), 3.69 (dd, J ¼ 10.8, 6.7 Hz,
1H, H-1a), 3.72 (dd, J ¼ 8.5, 0.9 Hz, 1H, H-3), 3.75 (dd, J ¼ 8.3, 0.9 Hz,
1H, H-4), 3.78 (ddd, J ¼ 8.5, 6.7, 2.8 Hz, 1H, H-2), 3.79 (dd, J ¼ 11.2,
3.7 Hz, 1H, H-6b), 3.83 (ddd, J ¼ 10.1, 4.4, 2.3 Hz, 1H, H-50), 4.13 (dd,
J ¼ 10.8, 2.8 Hz, 1H, H-1b), 4.15 (dd, J ¼ 12.4, 2.3 Hz, 1H, H-60a), 4.28
(dd, J ¼ 12.4, 4.4 Hz, 1H, H-60b), 4.92 (d, J ¼ 0.9 Hz, 1H, H-10), 5.16
(dd, J ¼ 10.1, 3.2 Hz, 1H, H-30), 5.30 (dd, J ¼ 10.1, 10.1 Hz, 1H, H-40),
0.7 Hz, 1H, H-20). 13C NMR (200 MHz, CD3OD)
d: 14.0/14.2 (2C)/14.3
(acyl CH3), 19.6 (COCH2CH2CH3), 23.32/23.35/23.4 [CO(CH2)3CH2
CH3], 25.4/25.57/25.61 [COCH2CH2(CH2)2CH3], 32.30/32.33/32.4
[CO(CH2)2CH2CH2CH3], 34.9 (3C) [COCH2(CH2)3CH3], 37.0
(COCH2CH2CH3), 63.1 (C-60), 65.2 (C-6), 66.9 (C-40), 70.5 (C-20), 71.1
(C-3), 71.2 (C-4), 71.7 (C-2), 72.7 (C-30), 73.0 (C-5), 73.5 (C-50), 73.7
(C-1), 100.5 (C-10), 173.9 (2C)/174.6/175.0 (OCOCH2). FABMS m/z (%):
731 ([M þ Na]þ, 48), 99 (100). FABHRMS calcd for C34H60O15Na
[M þ Na]þ: 731.3830; found: 731.3834.
25
3.1.26.3. Compound 2l. Colorless amorphous. [
a]
ꢁ 28.3 (c 1.08,
5.51 (dd, J ¼ 3.2, 0.9 Hz, 1H, H-20). 13C NMR (200 MHz, CD3OD)
d:
D
CHCl3). IR (neat) cmꢁ1: 3391, 1748, 1458, 1420, 1377, 1246, 1169,
14.2 (2C)/14.3/14.5 (acyl CH3), 23.35/23.37/23.40/23.7 (acyl CH2),
25.4/25.58/25.62/26.3 (COCH2CH2), 30.2/30.4/30.6 [CO(CH2)2(CH2)3
(CH2)2CH3], 32.3/32.36/32.45/33.1 (acyl CH2), 34.85/34.93/35.0/
35.2 (COCH2), 63.1 (C-60), 65.2 (C-6), 66.8 (C-40), 70.5 (C-20), 71.1 (C-
3), 71.2 (C-4), 71.7 (C-2), 72.7 (C-30), 73.0 (C-5), 73.5 (C-50), 73.7 (C-
1), 100.6 (C-10), 173.8/173.9/174.8/175.0 (OCOCH2). FABMS m/z (%):
801 ([M þ Na]þ, 100). FABHRMS calcd for C39H70O15Na [M þ Na]þ:
801.4612; found: 801.4601.
1096,1069. 1H NMR (800 MHz, CD3OD)
d
: 0.90 (t, J ¼ 7.3 Hz, 6H, acyl
CH3), 0.92/0.96 (each t, J ¼ 7.3 Hz, 3H, acyl CH3), 1.24e1.40 [m, 12H,
CO(CH2)2(CH2)2CH3], 1.40e1.45 [m, 2H, CO(CH2)2CH2CH3],
1.51e1.59 (m, 4H, COCH2CH2), 1.62e1.68 (m, 4H, COCH2CH2), 2.19/
2.21/2.27/2.31/2.34/2.37 [each dt,
COCH2(CH2)3CH3], 2.42/2.47 [each dt,
J
¼
15.8, 7.6 Hz, 1H,
15.6, 7.4 Hz, 1H,
J
¼
COCH2(CH2)2CH3], 3.61 (dd, J ¼ 11.3, 6.0 Hz, 1H, H-6a), 3.66 (ddd,
J ¼ 8.2, 6.0, 3.7 Hz,1H, H-5), 3.69 (dd, J ¼ 10.8, 6.4 Hz,1H, H-1a), 3.72
(dd, J ¼ 8.5, 1.1 Hz, 1H, H-3), 3.75 (dd, J ¼ 8.2, 1.1 Hz, 1H, H-4), 3.78
(ddd, J ¼ 8.5, 6.4, 2.7 Hz, 1H, H-2), 3.79 (dd, J ¼ 11.3, 3.7 Hz, 1H, H-
6b), 3.83 (ddd, J ¼ 9.9, 4.4, 2.3 Hz,1H, H-50), 4.13 (dd, J ¼ 10.8, 2.7 Hz,
1H, H-1b), 4.15 (dd, J ¼ 12.4, 2.3 Hz, 1H, H-60a), 4.27 (dd, J ¼ 12.4,
4.4 Hz, 1H, H-60b), 4.92 (d, J ¼ 0.9 Hz, 1H, H-10), 5.16 (dd, J ¼ 10.1,
3.2 Hz,1H, H-30), 5.29 (dd, J ¼ 10.1, 9.9 Hz,1H, H-40), 5.51 (dd, J ¼ 3.2,
25
3.1.26.6. Compound 2o. Colorless amorphous. [
a
]
ꢁ 27.3 (c 1.09,
D
CHCl3). IR (neat) cmꢁ1: 3383, 1748, 1458, 1416, 1377, 1246, 1169,
1103, 1069. 1H NMR (800 MHz, CD3OD)
: 0.90 (t, J ¼ 7.1 Hz, 9H, acyl
d
CH3), 0.92 (t, J ¼ 7.1 Hz, 3H, acyl CH3), 1.24e1.43 (m, 24H, acyl CH2),
1.51e1.59 (m, 4H, COCH2CH2), 1.63e1.70 (m, 4H, COCH2CH2), 2.19/
2.21/2.27/2.31 (each dt, J ¼ 15.8, 7.3 Hz, 1H, COCH2), 2.34/2.37 (each
dt, J ¼ 15.8, 7.6 Hz, 1H, COCH2), 2.39/2.48 (each dt, J ¼ 15.4, 7.3 Hz,
1H, COCH2), 3.61 (dd, J ¼ 11.2, 6.0 Hz, 1H, H-6a), 3.66 (ddd, J ¼ 8.2,
6.0, 3.4 Hz, 1H, H-5), 3.69 (dd, J ¼ 10.8, 6.7 Hz, 1H, H-1a), 3.72 (dd,
J ¼ 8.5, 0.9 Hz, 1H, H-3), 3.75 (dd, J ¼ 8.2, 0.9 Hz, 1H, H-4), 3.78 (ddd,
J ¼ 8.5, 6.7, 2.7 Hz,1H, H-2), 3.79 (dd, J ¼ 11.2, 3.4 Hz,1H, H-6b), 3.83
(ddd, J ¼ 9.8, 4.1, 2.3 Hz, 1H, H-50), 4.13 (dd, J ¼ 10.8, 2.7 Hz, 1H, H-
1b), 4.15 (dd, J ¼ 12.4, 2.3 Hz, 1H, H-60a), 4.28 (dd, J ¼ 12.4, 4.1 Hz,
1H, H-60b), 4.92 (d, J ¼ 1.0 Hz, 1H, H-10), 5.16 (dd, J ¼ 10.1, 3.3 Hz, 1H,
H-30), 5.30 (dd, J ¼ 10.1, 9.8 Hz, 1H, H-40), 5.51 (dd, J ¼ 3.3, 1.0 Hz, 1H,
0.9 Hz, 1H, H-20). 13C NMR (200 MHz, CD3OD)
d: 14.1/14.2 (2C)/14.3
(acyl CH3), 23.2/23.3/23.36/23.38 (acyl CH2), 25.4/25.58/25.62
[COCH2CH2(CH2)2CH3], 28.3 (COCH2CH2CH2CH3), 32.3 (2C)/32.4
[CO(CH2)2CH2CH2CH3], 34.8/34.90/34.92/34.93 (COCH2), 63.1 (C-
60), 65.2 (C-6), 66.9 (C-40), 70.5 (C-20), 71.1 (C-3), 71.2 (C-4), 71.7 (C-
2), 72.7 (C-30), 73.0 (C-5), 73.5 (C-50), 73.7 (C-1), 100.6 (C-10), 173.9
(2C)/174.8/175.0 (OCOCH2). FABMS m/z (%): 745 ([M þ Na]þ, 49), 99
(100). FABHRMS calcd for C35H62O15Na [M þ Na]þ: 745.3986;
found: 745.3992.
H-20). 13C NMR (200 MHz, CD3OD)
d: 14.21/14.22/14.3/14.5 (acyl
3.1.26.4. Compound 2m. Colorless amorphous. [
a
]
25 ꢁ 26.7 (c 1.02,
CH3), 23.36/23.37/23.40/23.7 (acyl CH2), 25.5/25.58/25.62
[COCH2CH2(CH2)2CH3], 26.4 [COCH2CH2(CH2)6CH3], 30.2/30.5/30.6/
30.7 [COCH2CH2(CH2)4(CH2)2CH3], 32.3/32.4/32.5/33.1 (acyl CH2),
34.85/34.94/35.0 [COCH2(CH2)3CH3], 35.2 [COCH2(CH2)7CH3], 63.1
(C-60), 65.2 (C-6), 66.8 (C-40), 70.5 (C-20), 71.1 (C-3), 71.2 (C-4), 71.7
(C-2), 72.8 (C-30), 73.0 (C-5), 73.5 (C-50), 73.7 (C-1), 100.6 (C-10),
173.7/173.9/174.8/175.0 (OCOCH2). FABMS m/z (%): 815 ([M þ Na]þ,
100). FABHRMS calcd for C40H72O15Na [M þ Na]þ: 815.4769; found:
815.4767.
D
CHCl3). IR (neat) cmꢁ1: 3387, 1748, 1462, 1416, 1377, 1273, 1242,
1165, 1099, 1069. 1H NMR (800 MHz, CD3OD)
d: 0.90 (t, J ¼ 7.3 Hz,
6H, acyl CH3), 0.916/0.922 (each t, J ¼ 7.3 Hz, 3H, acyl CH3),
1.24e1.44 (m, 18H, acyl CH2), 1.51e1.59 (m, 4H, COCH2CH2),
1.62e1.70 (m, 4H, COCH2CH2), 2.19/2.21/2.27/2.31/2.34/2.37 (each
dt, J ¼ 15.8, 7.6 Hz, 1H, COCH2), 2.40/2.47 (each dt, J ¼ 15.3, 7.4 Hz,
1H, COCH2), 3.61 (dd, J ¼ 11.2, 6.0 Hz, 1H, H-6a), 3.66 (ddd, J ¼ 8.2,
6.0, 3.7 Hz, 1H, H-5), 3.69 (dd, J ¼ 10.8, 6.7 Hz, 1H, H-1a), 3.72 (dd,
J ¼ 8.4, 0.9 Hz, 1H, H-3), 3.75 (dd, J ¼ 8.2, 0.9 Hz, 1H, H-4), 3.78 (ddd,
J ¼ 8.4, 6.7, 2.8 Hz, 1H, H-2), 3.78 (dd, J ¼ 11.2, 3.7 Hz, 1H, H-6b), 3.83
(ddd, J ¼ 10.1, 4.3, 2.3 Hz, 1H, H-50), 4.13 (dd, J ¼ 10.8, 2.8 Hz, 1H, H-
1b), 4.15 (dd, J ¼ 12.4, 2.3 Hz, 1H, H-60a), 4.27 (dd, J ¼ 12.4, 4.3 Hz,
1H, H-60b), 4.92 (d, J ¼ 0.7 Hz,1H, H-10), 5.16 (dd, J ¼ 10.1, 3.2 Hz,1H,
H-30), 5.29 (dd, J ¼ 10.1, 10.1 Hz, 1H, H-40), 5.51 (dd, J ¼ 3.2, 0.7 Hz,
25
3.1.26.7. Compound 2p. Colorless amorphous. [
a
]
ꢁ 24.9 (c 0.98,
D
CHCl3). IR (neat) cmꢁ1: 3383, 1748, 1458, 1416, 1377, 1242, 1169,
1103, 1069. 1H NMR (500 MHz, CD3OD)
: 0.90 (t, J ¼ 6.9 Hz, 3H, acyl
d
CH3), 0.91 (t, J ¼ 6.9 Hz, 6H, acyl CH3), 0.93 (t, J ¼ 6.9 Hz, 3H, acyl
CH3), 1.22e1.40 (m, 26H, acyl CH2), 1.52e1.61 (m, 4H, COCH2CH2),
1.62e1.72 (m, 4H, COCH2CH2), 2.19/2.22 (each dt, J ¼ 15.6, 7.5 Hz,
1H, COCH2), 2.27/2.32 (each dt, J ¼ 15.9, 7.3 Hz, 1H, COCH2), 2.34/
2.38 (each dt, J ¼ 15.8, 7.4 Hz, 1H, COCH2), 2.40/2.49 (each dt,
J ¼ 15.3, 7.2 Hz, 1H, COCH2), 3.62 (dd, J ¼ 11.0, 6.0 Hz, 1H, H-6a), 3.67
(ddd, J ¼ 8.0, 6.0, 3.3 Hz, 1H, H-5), 3.70 (dd, J ¼ 10.6, 6.6 Hz, 1H, H-
1a), 3.73 (dd, J ¼ 8.6, 1.0 Hz, 1H, H-3), 3.76 (dd, J ¼ 8.0, 1.0 Hz, 1H, H-
4), 3.79 (ddd, J ¼ 8.6, 6.6, 2.6 Hz, 1H, H-2), 3.80 (dd, J ¼ 11.0, 3.3 Hz,
1H, H-20). 13C NMR (200 MHz, CD3OD)
d: 14.2 (2C)/14.3/14.5 (acyl
CH3), 23.3/23.37/23.39/23.6 (acyl CH2), 25.4/25.58/25.62/26.3
(COCH2CH2), 29.9 [CO(CH2)2CH2(CH2)2CH3], 32.3 (2C)/32.4/32.8
(acyl CH2), 34.87/34.93/35.0/35.2 (COCH2), 63.1 (C-60), 65.2 (C-6),
66.9 (C-40), 70.5 (C-20), 71.1 (C-3), 71.2 (C-4), 71.7 (C-2), 72.7 (C-30),
73.0 (C-5), 73.5 (C-50), 73.7 (C-1), 100.6 (C-10), 173.8/173.9/174.8/
175.0 (OCOCH2). FABMS m/z (%): 773 ([M þ Na]þ, 100). FABHRMS