Total Synthesis of Neolignan Compounds
J. Chin. Chem. Soc., Vol. 51, No. 5A, 2004 1003
room temperature, then it was filtered. The benzene/acetone
was distilled off then, the residue was flash chromatographed
using petroleum ether ethyl acetate (3:1, v/v) as eluent where
108 mg yellow solid of Eusiderin K was obtained. mp.: 85-87
°C; EI-MS (m/z): 372 (M+, 15), 194 (100), 179 (9); 1H-NMR
(400 MHz, DCCl3): d 1.24 (d, J = 6.7 Hz, 3H, 9-H), 3.30 (d, J
= 6.4 Hz, 2H, 7¢-H), 3.64 (s, 3H, -OMe), 3.91 (s, 6H, 2X-
OMe), 4.05-4.13 (m, 1H, 8-H), 4.52 (d, J = 7.7 Hz, 1H, 7-H),
5.16 (d, J = 13.8 Hz, 2H, -CH2CH=CH2), 5.87-5.97 (m, 1H,
-CH2-CH=CH2), 6.35-6.63 (m, 4H, Ar-H); 13C-NMR (400
MHz): d 132.3 (1-C), 104.2 (2-C), 147.2 (3-C), 135.3 (4-C),
147.2 (5-C), 104.2 (6-C), 81.1 (7-C), 74.2 (8-C), 17.3 (9-C),
132.1 (1¢-C), 109.6 (2¢-C), 144.3 (3¢-C), 131.3 (4¢-C), 148.5
(5¢-C), 102.9 (6¢-C), 44.6 (7¢-C), 137.3 (8¢-C), 115.8 (9¢-C),
56.4, 56.1 (OMe); Found: C, 67.55; H, 6.48. C21H24O6 re-
quires C, 67.67; H, 6.50%.
13C-NMR (400 MHz): d 136.0 (1-C), 107.5 (2-C), 149.7
(3-C), 137.3 (4-C), 149.7 (5-C), 104.2 (6-C), 85.8 (7-C), 78.6
(8-C), 21.6 (9-C), 136.1 (1¢-C), 108.3 (2¢-C), 143.0 (3¢-C),
138.0 (4¢-C), 143.0 (5¢-C), 102.9 (6¢-C), 128.5 (7¢-C), 119.9
(8¢-C), 22.6 (9¢-C), 60.5, 64.8 (OMe); Found: C, 68.37; H,
6.73. C22H26O6 requires C, 68.38; H, 6.78%.
The above data were consistent with the literature.1
Eusiderin F
The synthesis of Eusiderin F was the same as that of J.
IR: n (cm-1, film): 723, 832, 915, 1000, 1037, 1131,
1230, 1287, 1331, 1458, 1593, 1689, 2845, 2926; EI-MS
(m/z): 386 (M+, 36), 208 (100), 194 (48), 193 (57), 191 (31),
179 (26); 1H-NMR (400 MHz, DCCl3): d 1.14 (d, J = 6.2 Hz,
3H, 9-H), 1.7 (dd, J = 1.6 Hz, 6.6 Hz, 3H, -CH=CHCH3),
4.05-4.13 (m, 1H, 8-H), 4.59 (d, J = 7.6 Hz, 1H, 7-H),
5.79-6.00 (m, 2H, -CH=CHMe), 6.36-6.79 (m, 4H, Ar-H);
13C-NMR (400 MHz): d 136.0 (1-C), 107.5 (2-C), 149.7
(3-C), 137.3 (4-C), 149.6 (5-C), 104.4 (6-C), 85.8 (7-C), 78.6
(8-C), 21.6 (9-C), 136.1 (1¢-C), 108.3 (2¢-C), 143.3 (3¢-C),
138.0 (4¢-C), 143.0 (5¢-C), 102.9 (6¢-C), 128.5 (7¢-C), 119.7
(8¢-C), 22.6 (9¢-C), 60.5, 64.7 (OMe); Found: C, 67.58; H,
6.42. C22H26O6 requires C, 67.67; H, 6.50%.
The above data were consistent with the literature.3
Eusiderin J
Eusiderin K (300 mg), 25 mL acetone, 45 mg KOH and
0.5 mL (CH3)2SO4 were added to a flask. After stirring for 8
h, the solution was filtered and the acetone was distilled off,
then the residure was flash chromatographed using petroleum
ether ethyl acetate (3:1, v/v) as eluent. A yellow liquid (296
mg) Eusiderin J was obtained. IR (n, cm-1, film): 623, 725,
831, 916, 1003, 1039, 1129, 1186, 1232, 1330, 1424, 1459,
1504, 1593, 1691, 2836, 2938; EI-MS (m/z): 386 (M+), 344,
302, 208, 193, 151, 149, 105; 1H-NMR (400 MHz, DCCl3): d
1.24 (d, J = 6.1 Hz, 3H, 9-H), 3.30 (d, J = 6.1 Hz, 2H, 7¢-H),
3.64 (s, 3H, -OMe), 3.91 (s, 9H, 3X-OMe), 4.05-4.13 (m, 1H,
8-H), 4.52 (d, J = 7.7 Hz, 1H, 7-H), 5.23 (d, J = 13.8 Hz, 2H,
-CH2CH=CH2), 5.87-5.97 (m, 1H, -CH2-CH=CH2), 6.35-
6.63 (m, 4H, Ar-H); 13C-NMR (400 MHz): d 131.2 (1-C),
100.3 (2-C), 148.6 (3-C), 137.3 (4-C), 144.3 (5-C), 106.8
(6-C), 76.9 (7-C), 74.1 (8-C), 12.6 (9-C), 131.3 (1¢-C), 109.6
(2¢-C), 144.3 (3¢-C), 132.5 (4¢-C), 153.5 (5¢-C), 104.6 (6¢-C),
40.0 (7¢-C), 137.3 (8¢-C), 115.8 (9¢-C), 56.3, 56.2 (OMe);
Found: C, 68.33; H, 6.70. C22H26O6 requires C, 68.38; H,
6.78%.
The above data were consistent with the literature.2
Compound 11
To a stirred solution of 10 (1 g, 5.55 mmol) in 50 mL
CH2Cl2 was added dropwise 0.53 mL Ac2O and a drop of
pyridine. After the solution was stirred overnight it was evap-
orated in a vacuum. Crude products were dissolved in water
and then extracted with Et2O (50 mL ´ 3). Then combined ex-
tracts were dissolved in 95% ethanol and then 0.6 g SeO2 was
added. After the solution was refluxed for 4 h, it was evapo-
rated in a vacuum; crude products were dissolved in water
and exacted with Et2O (50 mL ´ 3). Then combined extracts
were dried (Na2SO4). The Et2O was distilled off. The residue
was flash chromatographed using petroleum ether and ethyl
acetate (10:1, v/v) as eluent to afford a yellow solid of 11 (1.1
g, yield 72% from 10). Mp.: 122-124 °C; EI-MS (m/z): 278
(M+, 40), 257 (20), 236 (10), 194 (100), 166 (60), 151 (40);
1H-NMR (80 MHz, CDCl3): d 1.89 (s, 6H, Ar-CO-Me), 3.86
(s, 3H, Ar-OMe), 6.4-6.6 (m, 4H, Ar-H, Ar-CH=CH-CHO),
9.4 (s, -CHO, 1H).
The above data were consistent with the literature.3
Eusiderin E
The synthesis of Eusiderin E was the same as that of K.
EI-MS (m/z): 372 (M+, 16), 245 (32), 194 (65), 180
(100); 1H-NMR (400 MHz, DCCl3): d 1.14 (d, J = 6.2 Hz, 3H,
9-H), 1.7 (dd, J = 1.6 Hz, 6.6 Hz, 3H, -CH=CHCH3),
4.05-4.13 (m, 1H, 8-H), 4.59 (d, J = 7.8 Hz, 1H, 7-H),
5.79-6.00 (m, 2H, -CH=CHMe), 6.36-6.79 (m, 4H, Ar-H);
Compound 12
A solution of 11 (1 g, 5.2 mmol) in 40 mL methanol and
20 mL water was treated with 20 mL saturated sodium bicar-
bonate solution and stirred at room temperature overnight un-