X.-X. Shi et al. / Tetrahedron: Asymmetry 19 (2008) 435–442
441
7.49 (d, J = 7.7 Hz, 1H), 7.31 (d, J = 8.1 Hz, 1H), 7.10 (dd,
J = 7.2 Hz; 7.9 Hz, 1H), 7.01 (dd, J = 7.7 Hz; 7.2 Hz, 1H),
6.86 (d, J = 8.0 Hz, 1H), 6.82 (s, 1H), 6.75 (d, J = 1.4 Hz,
1H), 6.60 (dd, J = 1.1 Hz; 8.0 Hz, 1H), 5.99 (d,
J = 6.5 Hz, 2H), 4.24 (d, J = 17.6 Hz, 1H), 4.07 (dd,
J = 4.1 Hz; 11.8 Hz, 1H), 4.03 (d, J = 17.7 Hz, 1H), 3.25
(dd, J = 4.2 Hz; 15.4 Hz, 1H), 2.95 (dd, J = 12.1 Hz;
14.8 Hz, 1H), 2.84 (s, 3H). 13C NMR (DMSO-d6) d
164.78, 162.37, 147.69, 147.33, 136.20, 132.92, 130.25,
125.94, 121.78. 118.99, 118.16, 111.36, 108.42, 108.21,
107.55, 101.32, 52.09, 50.94, 50.73, 32.69, 26.74. MS
(m/z, relative intensity) 390 (M++1, 17), 389 (M+, 100),
360(1), 317(4), 289(7), 268(7), 262(26), 233(8), 204(8),
169(3), 115(1), 102(1). IR (KBr film) 3314, 2924, 1711,
1659, 1623, 1488, 1468, 1450, 1328, 1291, 1267, 1237,
1159, 1037, 931, 875, 789, 740, 607 cmꢁ1. Anal. Calcd for
C22H19N3O4: C, 67.86; H, 4.92; N, 10.79. Found: C,
67.82; H, 4.83; N, 10.73.
temperature for 6.5 h. After THF was removed by distilla-
tion under reduced pressure, the residual oil was cooled to
room temperature and diluted with 45 mL of 0.5 M HCl
aqueous solution. The white solid precipitated and was fil-
tered to give crude product which was purified by flash
chromatography (eluent: ethyl acetate–dichloromethane–
petroleum ether = 1:2:6) to afford compound 3 (502 mg,
1.28 mmol) in 33% yield and compound 4 (990 mg,
2.52 mmol) in 65% yield. After two recrystallizations in
1,2-dichloroethane, compound 3 was characterized as fol-
20
1
lows: ½aꢀD ¼ þ87:1 (c 1.0, CHCl3). H NMR (CDCl3) d
7.84 (s, 1H), 7.61 (d, J = 7.0 Hz, 1H), 7.27 (d, J = 9.0 Hz,
1H), 7.13–7.21 (m, 2H), 6.86 (dd, J = 1.7 Hz; 8.0 Hz,
1H), 6.73 (d, J = 1.7 Hz, 1H), 6.69 (d, J = 8.0 Hz, 1H),
6.15 (s, 1H), 5.87 (dd, J = 1.4 Hz; 11.6 Hz, 1H), 4.30 (dd,
J = 4.3 Hz; 11.6 Hz, 0.16H at C-6 position), 4.09 (s,
0.10H at C-3 position), 3.93 (s, 0.10H at C-3 position),
3.78 (d, J = 16.0 Hz, 1H), 3.21 (d, J = 15.9 Hz, 1H), 3.04
(s, 3H). MS (m/z, relative intensity) 393 (M++1, 24), 392
(M+, 100), 391 (M+ꢁ1, 47), 363(2), 333(1), 318(10),
306(2), 290(11), 276(6), 276(6), 271(20), 262(74), 251(2),
243(4), 233(30), 218(3), 204(2), 170(21), 141(2), 131(3),
116(6), 102(8), 89(2), 77(2), 63(2), 46(6). IR (KBr film)
3323, 2902, 1672, 1645, 1626, 1488, 1423, 1396, 1329,
1242, 1155, 1099, 1038, 938, 920, 790, 745, 694, 625, 475,
4.8. (6R,12aS)-2,3,6,7,12,12a-Hexahydro-2-methyl-6-(3,4-
methylenedioxyphenyl)-3,3,12a-trideutero-pyrazino-
[20,10:6,1]pyrido[3,4-b]indole-1,4-dione 4
Compound 1 (0.50 g, 1.28 mmol), DMSO-d6 (1.5 mL),
THF (6 mL), D2O (1 mL), and anhydrous potassium car-
bonate (177 mg, 1.28 mmol) were mixed together. The mix-
ture was stirred and then heated at 65 °C. A clear solution
was obtained, and the stirring was continued at this tem-
perature for 16 h. Afterwards THF was removed by distil-
lation under reduced pressure, the residual oil was cooled
to room temperature and diluted with 25 mL of 0.5 M
HCl aqueous solution. The white solid precipitated and
was filtered to give crude product which was purified by
flash chromatography to afford compound 4 (0.48 g,
1.22 mmol) in 95% yield. After two recrystallizations in
1,2-dichloroethane, compound 4 was characterized as fol-
435 cmꢁ1
(M+), 392.1564; found: 392.1565.
. HRMS(EI) m/z calcd for C22H16D3N3O4
Acknowledgments
We thank the Chinese National Natural Science Founda-
tion (No. A-20172015) and the Shanghai Educational
Development Foundation (The Dawn Program: No.
03SG27) for financial support of this work.
20
1
lows: ½aꢀD ¼ ꢁ268:0 (c 1.2, CHCl3). H NMR (CDCl3) d
8.08 (s, NH on the indole ring), 7.53 (d, J = 7.8 Hz, 1H),
7.32 (d, J = 8.0 Hz), 7.22 (dd, J = 7.9 Hz; 8.1 Hz, 1H),
7.16 (dd, J = 7.2 Hz; 7.1 Hz, 1H), 6.97 (s, 1H), 6.80 (s,
1H), 6.70 (s, 2H), 5.92 (d, J = 3.6 Hz, 2H), 4.34 (dd,
J = 4.1 Hz; 11.9 Hz, 0.16H at C-6 position), 4.13 (s,
0.06H at C-3 position), 3.98 (s, 0.06H at C-3 position),
3.54 (d, J = 15.4 Hz, 1H), 2.99 (s, 3H), 2.94 (d,
J = 15.6 Hz, 1H). MS (m/z, relative intensity) 393
(M++1, 28), 392 (M+, 100), 391 (M+ꢁ1, 24), 363(2),
333(1), 318(7), 290(14), 271(14), 262(73), 233(29), 204(30),
170(15), 141(3), 116(6), 102(6), 89(2), 77(1), 63(1), 46(4).
IR (KBr film) 3325, 2918, 1662, 1642, 1620, 1554, 1501,
1487, 1441, 1403, 1273, 1239, 1095, 1038, 924, 872, 823,
745, 653, 606, 425 cmꢁ1. HRMS(EI) m/z calcd for
C22H16D3N3O4 (M+), 392.1564; found: 392.1526.
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