ORDER
REPRINTS
3
426
WANG ET AL.
1
896, 1754, 1645, 1621, 1490, 1439, 1371, 1239, 1038, 909, 731; H-NMR
2
(
7
400 MHz, CDCl ): d ppm 8.24 (1H, d, J ¼ 8 Hz, H-5), 7.93 (1H, s, H-2),
3
0
0
.09 (1H, d, J ¼ 1.0 Hz, H-2 ), 7.06 (1H, d, J ¼ 2.0 Hz, H-6 ), 7.03 (1H, d,
J ¼ 6.0 Hz, H-8), 6.97(1H, dd, J ¼ 8.6, 2.0 Hz, H-6), 6.87(1H, J ¼ 8.0 Hz, H-
0
00 00
), 6.0 (2H, s, -OCH O-), 5.3 (1H, m, H-1 ), 5.23 (1H, m, H-3 ), 5.20 (1H,
2
5
00
00
m, H-2 ), 4.30 (1H, dd, J ¼ 12.0, 2.0 Hz, H-6 a), 4.20 (1H, dd, J ¼ 12.0,
00 00 00
2
.0 Hz, H-6 b), 3.97(1H, m, H-5 ), 3.94 (1H, m, H-4 ), 2.1 (12H, m,
1
3
CH CO-); C-NMR (100 MHz, CDCl ): d ppm 175.5 (C-4), 170.4, 170.1,
3
3
0
1
1
4
69.3, 169.2 (-CO-), 169.2 (C-7), 157.3 (C-8a), 152.4 (C-2), 147.8 (C-3 ),
0
0
0
47.8 (C-4 ), 28.2 (C-5), 125.3 (C-3), 125.3 (C-1 ), 122.3 (C-6 ), 120.2 (C-
0
0
00
a), 115.3 (C-6), 109.7(C-2 ), 108.4 (C-5 ), 104.3 (C-8), 104.2 (C-1 ), 101.2 (-
00
00
00
00
00
OCH O-), 77.3 (C-5 ), 76.8 (C-3 ), 71.0 (C-2 ), 68.2 (C-4 ), 62.0 (C-6 ), 20.6
2
þ
(
(
-CH ); EI-MS (m/z): 612 (M , 3), 170 (9), 69 (100), 145 (11), 139 (9), 129
3
21), 115 (3), 109 (71), 97 (8), 85 (5), 81 (7), 69 (4), 43 (87).
Ononin (1a)
In a 5 mL round-bottomed flask, 3a (65 mg, 0.109 mmol) was dissolved
in methanol (2 mL), anhydrous zinc acetate (23 mg, 0.126 mmol) was added
to the stirring solution. The mixture was refluxed for 7h (monitored by
TLC). After cooled down at RT the mixture was filtered by cation exchange
resin, the solvent was evaporated under vacuum. The residue was purified by
silica gel flash chromatography (CHCl : MeOH 12 : 1 v/v) to get the product
3
ꢀ
À1
1
2
a 45 mg, yield: 96%, white solids, mp. 203–205 C; IR: (KBr) cm 3404,
1
924, 2853, 1629, 1570, 1513, 1444, 1252, 1194, 1074, 1017, 819; H-NMR
(
400 MHz, DMSO-d ): d ppm 8.43 (1H, s. H-2), 8.06 (1H, d, J ¼ 9.0 Hz,
6
0 0
H-5), 7.53 (2H, dd, J ¼ 8.7, 2.0 Hz, H-2 , 6 ), 7.23 (1H, d, J ¼ 2.3 Hz, H-8),
0
0
7
5
5
-
3
.14 (1H, dd, J ¼ 9.0, 2.3 Hz, H-6), 6.98 (2H, dd, J ¼ 8.7, 2.0 Hz, H-3 , 5 ),
00 00 00
.41 (1H, d, 2 -OH), 5.10–5.13 (1H, m, 3 -OH), 5.06–5.09 (1H, m, 4 -OH),
0
0
00
.06 (1H, d, J ¼ 5.2 Hz, H-1 ), 4.58–4.61 (1H, m, 6 -OH), 3.78 (3H, s,
00 00 00
OCH ), 3.69–3.70 (1H, m, H-5 , 6 a), 3.43–3.48 (1H, m, H-6 b),
3
00
00
00
13
.28–3.32 (1H, m, H-2 , 3 ), 3.16–3.20 (1H, m, H-4 );
C-NMR
0
(
100 MHz, DMSO-d ): d ppm 174.6 (C-4), 161.4 (C-7), 159 (C-4 ), 157.0
6
0
0
0
(
1
(
C-8a), 153.5 (C-2), 130.0 (C-2 , 6 ), 127.0 (C-5), 124.0 (C-3), 123.3 (C-1 ),
0 0 00
18.4 (C-4a), 115.6 (C-6), 113.6 (C-3 , 5 ), 103.4 (C-8), 100 (C-1 ), 77.2
C-5) , 76.4 (C-3 ), 73.1 (C-2 ), 69.6 (C-4 ), 60.6 (C-6 ), 55.1 (-OCH );
00
00
00
00
00
3
þ
FAB-MS (m/z): 430 [M ].
Using the above procedure, rothindin 1b was obtained in 92% yield as
white solids, mp. 213–215 C; IR: (KBr) cm 3430, 2926, 1623, 1501, 1439,
1
1
ꢀ
À1
248, 1074, 1014, 920, 810; H-NMR (400 MHz, DMSO-d ): d ppm 8.45
6
0
(
1H, s, H-2), 8.05 (1H, d, J ¼ 9.0 Hz, H-5), 7.24 (1H, d, J ¼ 2.0 Hz, H-2 ),