10.1002/ejoc.201801842
European Journal of Organic Chemistry
FULL PAPER
168.26, 150.66, 144.89, 138.97, 136.39, 130.74, 129.78, 128.93, 125.50,
122.40, 119.10, 74.64, 47.11, 35.94, 29.55, 25.95, 21.57. IR (KBr) 2362,
1631, 1557, 1396, 1143, 670, 537 cm-1; HRMS (ESI) m/z: calculated for
C19H20ClN2O2S+ [M+H]+ 375.0929, found 375.0926.
4a-chloro-1-((4-(trifluoromethyl)phenyl)sulfonyl)-2,3,4,4a-tetrahydro-
1H-pyrido[2,3-b]indole (3o): White solid (57 mg, 45%); m.p. 140 – 141
oC; 1H NMR (400 MHz, CDCl3) δ 8.45 – 8.30 (m, 2H), 7.82 (d, J = 8.2-Hz,
2H), 7.46 (d, J = 7.8 Hz, 1H), 7.34 (t, J = 7.4 Hz, 2H), 7.18 (t, J = 7.4 Hz,
1H), 4.42 – 4.31 (m, 1H), 3.22 (td, J = 11.0, 3.8 Hz, 1H), 2.76 – 2.49 (m,
2H), 2.12 – 1.86 (m, 1H), 1.83 – 1.63 (m, 1H). 13C NMR (100 MHz,
CDCl3) δ 166.92, 151.19, 140.61, 137.17, 135.22 (q, J = 33.0 Hz), 130.38,
129.87, 125.80 (q, J = 3.6 Hz), 123.63 (d, J = 177.0 Hz), 122.09, 121.79,
120.76, 67.69, 47.79, 33.11, 21.32. 19F NMR (376 MHz, CDCl3) δ -63.18.
IR (KBr) 2428, 1588, 1324, 1171, 1127, 1062, 768, 713, 530 cm-1;
HRMS-(ESI) m/z: calculated for C18H15ClF3N2O2S+ [M+H]+ 415.0489,
found 415.0496.
4a-chloro-1-(o-tolylsulfonyl)-2,3,4,4a-tetrahydro-1H-pyrido[2,3-
b]indole (3j): White solid (92 mg, 85%); m.p. 111 – 112 oC; 1H NMR
(600 MHz, CDCl3) δ 8.25 (d, J = 8.0 Hz, 1H), 7.47 (td, J = 7.6, 1.0 Hz,
1H), 7.38 (d, J = 7.8 Hz, 1H), 7.34 (t, J = 7.8 Hz, 1H), 7.32 – 7.27 (m, 3H),
7.12 (td, J = 7.6, 1.0 Hz, 1H), 4.34 – 4.29 (m, 1H), 3.69 – 3.61 (m, 1H),
2.75 (s, 3H), 2.66 (dt, J = 4.8, 4.2 Hz, 1H), 2.57 – 2.47 (m, 1H), 2.08 –
2.00 (m, 1H), 1.94 – 1.87 (m, 1H). 13C NMR (150 MHz, CDCl3) δ 166.74,
151.68, 138.86, 136.90, 135.35, 133.83, 132.36, 132.33, 130.28, 125.70,
125.23, 121.87, 120.64, 68.18, 45.90, 32.91, 20.96, 20.49. IR (KBr) 2434,
1580, 1331, 1172, 1083, 1002, 857, 759, 533 cm-1; HRMS (ESI) m/z:
calculated for C18H18ClN2O2S+ [M+H]+ 361.0772, found 361.0780.
4a-chloro-1-((4-nitrophenyl)sulfonyl)-2,3,4,4a-tetrahydro-1H-
pyrido[2,3-b]indole (3p): White solid (68 mg, 58%); m.p. 146 – 147 oC;
1H NMR (400 MHz, CDCl3) δ 8.48 – 8.36 (m, 4H), 7.45 (d, J = 8.4 Hz,
1H), 7.35 (t, J = 7.0 Hz, 2H), 7.19 (t, J = 7.2 Hz, 1H), 4.43 – 4.36 (m, 1H),
3.25 (td, J = 11.2, 4.0 Hz, 1H), 2.70 – 2.56 (m, 2H), 2.05 – 1.94 (m, 1H),
1.82 – 1.71 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 166.78, 151.01,
150.66, 142.80, 137.13, 130.73, 130.47, 125.97, 123.83, 122.16, 120.82,
67.63, 47.90, 33.13, 21.35. IR (KBr) 2360, 1587, 1369, 1181, 1138, 1087,
776, 738, 531 cm-1; HRMS (ESI) m/z: calculated for C17H15ClN3O4S+
[M+H]+ 392.0466, found 392.0447.
4a-chloro-1-(phenylsulfonyl)-2,3,4,4a-tetrahydro-1H-pyrido[2,3-
b]indole (3k): White solid (84 mg, 81%); m.p. 118 – 119 oC; 1H NMR
(600 MHz, CDCl3) δ 8.23 (d, J = 7.4 Hz, 2H), 7.62 (t, J = 7.4 Hz, 1H),
7.54 (t, J = 7.8 Hz, 2H), 7.47 (d, J = 7.8 Hz, 1H), 7.36 – 7.29 (m, 2H),
7.15 (t, J = 7.6 Hz, 1H), 4.37 – 4.29 (m, 1H), 3.28 (td, J = 11.2, 4.2 Hz,
1H), 2.68 – 2.51 (m, 2H), 1.99 – 1.90 (m, 1H), 1.80 – 1.71 (m, 1H). 13C
NMR (150 MHz, CDCl3) δ 167.08, 151.54, 137.20, 137.05, 133.71,
130.26, 129.20, 128.66, 125.43, 121.96, 120.66, 67.82, 47.38, 33.01,
21.18. IR (KBr) 2360, 1575, 1360, 1180, 1165, 1089, 774, 752, 567 cm-1;
HRMS (ESI) m/z: calculated for C17H16ClN2O2S+ [M+H]+ 347.0616, found
347.0613.
10b-chloro-5-tosyl-10b,11-dihydro-5H-indolo[2,3-b]quinolone (3q):
o
1
Light green solid (35 mg, 28%); m.p. 146 – 147 C; H NMR (400 MHz,
CDCl3) δ 8.03 (d, J = 8.2 Hz, 1H), 7.77 (d, J = 8.4 Hz, 2H), 7.52 – 7.40 (m,
2H), 7.37 – 7.28 (m, 3H), 7.23 (d, J = 7.6 Hz, 1H), 7.20 – 7.09 (m, 3H),
3.26 (d, J = 16.2 Hz, 1H), 2.57 (d, J = 16.2 Hz, 1H), 2.34 (s, 3H). 13C
NMR (100 MHz, CDCl3) δ 165.87, 152.36, 145.13, 135.76, 135.46,
135.07, 130.54, 129.23, 129.13, 128.89, 128.14, 127.14, 126.02, 125.23,
125.14, 122.15, 120.27, 67.65, 37.25, 21.66. IR (KBr) 2363, 1637, 1376,
1139, 994, 865, 763, 532, cm-1; HRMS (ESI) m/z: calculated for
C22H18ClN2O2S+ [M+H]+ 409.0772, found 409.0781.
4a-chloro-1-((4-chlorophenyl)sulfonyl)-2,3,4,4a-tetrahydro-1H-
pyrido[2,3-b]indole (3l): White solid (93 mg, 81%); m.p. 127 – 128 C;
o
1H-NMR (600 MHz, CDCl3) δ 8.20 – 8.16 (m, 2H), 7.53 – 7.49 (m, 2H),
7.47 – 7.43 (m, 1H), 7.35 – 7.30 (m, 2H), 7.16 (t, J = 7.6 Hz, 1H), 4.35 –
4.30 (m, 1H), 3.24 (td, J = 11.4, 4.2 Hz, 1H), 2.67 – 2.52 (m, 2H), 2.00 –
1.90 (m, 1H), 1.79 – 1.71 (m, 1H). 13C NMR (150 MHz, CDCl3) δ 167.00,
151.32, 140.38, 137.16, 135.47, 130.76, 130.32, 128.97, 125.60, 122.03,
120.66, 67.76, 47.54, 33.05, 21.23. IR (KBr) 2357, 1577, 1370, 1170,
1142, 1093, 774, 764, 532 cm-1; HRMS (ESI) m/z: calculated for
C17H15Cl2N2O2S+ [M+H]+ 381.0226, found 381.0217.
4a-chloro-7-fluoro-1-tosyl-2,3,4,4a-tetrahydro-1H-pyrido[2,3-b]indole
(3r): White solid (92 mg, 81%); m.p. 117 – 118 oC; 1H NMR (400 MHz,
CDCl3) δ 8.12 – 8.03 (m, 2H), 7.34 (d, J = 8.0 Hz, 2H), 7.29 – 7.24 (m,
1H), 7.16 (dd, J = 9.0, 2.4 Hz, 1H), 6.85 – 6.79 (m, 1H), 4.37 – 4.27 (m,
1H), 3.34 (td, J = 11.8, 11.2, 4.4 Hz, 1H), 2.67 – 2.49 (m, 2H), 2.43 (s,
3H), 2.00 – 1.90 (m, 1H), 1.81 – 1.68 (m, 1H). 13C NMR (100 MHz,
CDCl3) δ 168.72, 164.14 (d, J = 247.4 Hz), 153.59 (d, J = 11.8 Hz),
144.94, 133.94, 132.91 (d, J = 3.2 Hz), 129.35, 129.25, 122.76 (d, J =
10.2 Hz), 111.65 (d, J = 23.4 Hz), 108.65 (d, J = 25.0 Hz), 67.37, 46.98,
32.81, 21.66, 20.94. 19F NMR (376 MHz, CDCl3) δ -109.96. IR (KBr)
2436, 1578, 1305, 1188, 1107, 1086, 815, 703, 548 cm-1; HRMS (ESI)
m/z: calculated for C18H17ClFN2O2S+ [M+H]+ 379.0678, found 379.0679.
1-((4-bromophenyl)sulfonyl)-4a-chloro-2,3,4,4a-tetrahydro-1H-
pyrido[2,3-b]indole (3m): White solid (96 mg, 74%); m.p. 127 – 128 oC;
1H NMR (600 MHz, CDCl3) δ 8.10 (d, J = 8.2 Hz, 2H), 7.68 (d, J = 8.4 Hz,
2H), 7.45 (d, J = 7.8 Hz, 1H), 7.38 – 7.29 (m, 2H), 7.16 (t, J = 7.6 Hz, 1H),
4.37 – 4.28 (m, 1H), 3.23 (td, J = 11.2, 3.8 Hz, 1H), 2.67 – 2.51 (m, 2H),
2.00 – 1.92 (m, 1H), 1.80 – 1.68 (m, 1H). 13C NMR (150 MHz, CDCl3) δ
166.99, 151.32, 137.16, 136.02, 131.96, 130.82, 130.33, 129.02, 125.61,
122.04, 120.67, 67.75, 47.56, 33.06, 21.24. IR (KBr) 2360, 1576, 1375,
1175, 1135, 1092, 774, 739, 527 cm-1; HRMS (ESI) m/z: calculated for
C17H15BrClN2O2S+ [M+H]+ 424.9721, found 424.9723.
4a-chloro-8-methyl-1-tosyl-2,3,4,4a-tetrahydro-1H-pyrido[2,3-
b]indole (3s): White solid (87 mg, 78%); m.p. 142 – 143 oC; 1H NMR
(400 MHz, CDCl3) δ 8.13 (d, J = 8.4 Hz, 2H), 7.33 (d, J = 8.2 Hz, 2H),
7.18 – 7.11 (m, 2H), 7.04 (t, J = 7.6 Hz, 1H), 4.42 – 4.31 (m, 1H), 3.18 (td,
J = 11.2, 3.8 Hz, 1H), 2.65 – 2.54 (m, 2H), 2.49 (s, 3H), 2.43 (s, 3H), 2.01
– 1.89 (m, 1H), 1.74 – 1.62 (m, 1H). 13C NMR (100 MHz, CDCl3) δ
166.10, 149.93, 144.64, 136.93, 133.98, 131.61, 130.10, 129.80, 129.00,
125.26, 119.35, 68.02, 47.77, 33.37, 21.66, 21.42, 16.59. IR (KBr) 2409,
1586, 1362, 1168, 1087, 815, 741, 585 cm-1; HRMS (ESI) m/z: calculated
for C19H20ClN2O2S+ [M+H]+ 375.0929, found 375.0922.
4a-chloro-1-((4-fluorophenyl)sulfonyl)-2,3,4,4a-tetrahydro-1H-
pyrido[2,3-b]indole (3n): White solid (64 mg, 58%); mp: 132 – 133 C;
o
1H NMR (600 MHz, CDCl3) δ 8.29 – 8.23 (m, 2H), 7.45 (d, J = 7.6 Hz,
1H), 7.37 – 7.29 (m, 2H), 7.21 (t, J = 8.6 Hz, 2H), 7.16 (t, J = 7.8 Hz, 1H),
4.37 – 4.29 (m, 1H), 3.24 (td, J = 11.4, 4.2 Hz, 1H), 2.67 – 2.52 (m, 2H),
1.99 – 1.92 (m, 1H), 1.79 – 1.71 (m, 1H). 13C NMR (100 MHz, DMSO-d6)
δ 167.84, 165.68 (d, J = 253.4 Hz), 151.21, 137.66, 133.26 (d, J = 2.8
Hz), 132.72 (d, J = 9.8 Hz), 130.95, 126.25, 123.14, 120.42, 116.81 (d, J
= 22.8 Hz), 69.56, 48.93, 32.48, 21.76. 19F NMR (376 MHz, CDCl3) δ -
103.33. IR (KBr) 2360, 1584, 1371, 1177, 1159, 995, 852, 823, 542 cm-1;
HRMS (ESI) m/z: calculated for C17H15ClFN2O2S+ [M+H]+ 365.0521,
found 365.0534.
tert-butyl
4a-chloro-2,3,4,4a-tetrahydro-1H-pyrido[2,3-b]indole-1-
carboxylate (3t): White solid (71 mg, 77%); m.p. 100 – 101 oC; 1H NMR
(400 MHz, CDCl3) δ 7.53 (d, J = 7.8 Hz, 1H), 7.41 – 7.32 (m, 2H), 7.21 –
7.16 (m, 1H), 4.30 – 4.20 (m, 1H), 3.45 – 3.35 (m, 1H), 2.71 – 2.63 (m,
1H), 2.50 – 2.35 (m, 1H), 1.97 – 1.83 (m, 2H), 1.57 (s, 9H). 13C NMR
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