The Journal of Organic Chemistry
Article
173−175 °C; 1H NMR (500 MHz, CDCl3) δ 7.93 (s, 1H), 7.23 (d, J =
8.1 Hz, 1H), 7.18 (d, J = 8.2 Hz, 1H), 7.14−7.09 (m, 5H), 7.06−6.99
(m, 2H), 6.96 (dt, J = 1.1, 7.5 Hz, 1H), 6.91−6.88 (m, 1H), 6.77 (d, J
= 8.1 Hz, 2H), 5.51 (s, 1H), 2.51 (s, 3H), 2.17 (s, 3H); 13C NMR (75
MHz, CDCl3) δ 159.0, 148.9, 142.7, 139.2, 136.4, 129.1, 128.5, 127.6,
126.6, 126.4, 125.3, 124.9, 124.3, 122.7, 121.8, 119.6, 119.0, 118.6,
115.9, 111.1, 33.6, 21.3, 18.9; IR (KBr) νmax 3370, 3052, 2920, 1636,
1489, 1316, 1287, 1238, 1143, 1088, 742, 671, 608 cm−1; HRMS (ESI)
calcd for C25H21NO3SNa (M + Na) 438.1140, found 438.1123.
5-Methoxy-3-[2-methyl-3-(phenylsulfonyl)-4H-chromen-4-yl]-1H-
indole (17a). Colorless solid (122 mg, 94%): Rf = 0.5 (40% ethyl
acetate in hexanes); mp 110−112 °C; 1H NMR (500 MHz, CDCl3) δ
7.80 (s, 1H), 7.27−7.25 (m, 2H), 7.22−7.19 (m, 1H), 7.15−7.11 (m,
2H), 7.08−7.06 (m, 2H), 7.03−6.97 (m, 4H), 6.72−6.70 (m, 2H),
5.50 (s, 1H), 3.70 (s, 3H), 2.51 (s, 3H); 13C NMR (75 MHz, CDCl3)
δ 159.3, 153.9, 149.0, 142.1, 131.9, 131.4, 129.2, 127.9, 127.7, 126.3,
125.7, 125.0, 124.1, 123.4, 118.7, 115.8, 115.5, 112.1, 111.8, 100.4,
55.6, 33.5, 18.9; IR (KBr) νmax 3388, 3061, 2927, 1636, 1583, 1485,
1452, 1299, 1230, 1146, 1088, 755, 629 cm−1; HRMS (ESI) calcd for
C25H21NO4SNa (M + Na) 454.1089, found 454.1084.
2H), 5.49 (s, 1H), 3.99 (q, J = 7.3 Hz, 2H), 2.53 (s, 3H), 2.16 (s, 3H),
1.38 (t, J = 7.3 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 158.8, 148.8,
142.5, 139.3, 136.0, 129.0, 128.4, 127.5, 126.3, 126.0, 125.6, 124.8,
124.5, 121.2, 119.1, 118.9, 117.4, 115.9, 109.1, 40.6, 33.4, 21.2, 19.0,
15.4; IR (KBr) νmax 3431, 3048, 2972, 2927, 1636, 1590, 1463, 1321,
1292, 1234, 1146, 765, 736, 696, 661 cm−1; HRMS (ESI) calcd for
C27H25NO3SNa (M + Na) 466.1453, found 466.1449.
2-Methyl-3-[2-methyl-3-(phenylsulfonyl)-4H-chromen-4-yl]-6-
nitro-1H-indole (20). Yellow solid (123 mg, 89%): Rf = 0.2 (40% ethyl
acetate in hexanes); mp 254−256 °C; 1H NMR (500 MHz, CDCl3) δ
8.06 (s, 1H), 8.03 (s, 1H), 7.86 (dd, J = 2.1, 8.9 Hz, 1H), 7.23 (d, J =
7.4 Hz, 2H), 7.15−7.12 (m, 2H), 7.08 (d, J = 8.2 Hz, 1H), 7.06 (d, J =
8.9 Hz, 1H), 6.98−6.95 (m, 4H), 5.56 (s, 1H), 2.65 (s, 3H), 2.56 (s,
3H); 13C NMR [75 MHz, (CD3)2SO + CDCl3] δ 158.6, 147.7, 141.0,
140.0, 137.9, 135.6, 131.2, 128.2, 127.2, 127.1, 125.1, 124.9, 124.3,
122.8, 115.4, 115.2, 113.5, 109.7, 31.1, 18.1, 11.0; IR (KBr) νmax 3376,
3051, 2924, 2362, 1643, 1479, 1326, 1231, 1151, 756, 719, 626 cm−1;
HRMS (ESI) calcd for C25H20N2O5SNa (M + Na) 483.0991, found
483.0998.
3-[6-Methoxy-2-methyl-3-(phenylsulfonyl)-4H-chromen-4-yl]-1H-
indole (21). Orange solid (128 mg, 99%): Rf = 0.4 (40% ethyl acetate
in hexanes); mp 172−174 °C (CH2Cl2/hexane); 1H NMR (400 MHz,
CDCl3) δ 7.90 (s, 1H), 7.26−7.22 (m, 3H), 7.19−7.15 (m, 2H), 7.10
(d, J = 2.3 Hz, 1H), 7.05 (t, J = 7.1 Hz, 1H), 7.00−6.95 (m, 3H),
6.92−6.88 (m, 1H), 6.66 (dd, J = 2.9, 8.9 Hz, 1H), 6.61 (d, J = 2.9 Hz,
1H), 5.50 (s, 1H), 3.64 (s, 3H), 2.50 (s, 3H); 13C NMR (75 MHz,
CDCl3) δ 159.6, 156.5, 143.1, 142.2, 136.4, 131.8, 127.9, 126.2, 125.4,
124.9, 122.7, 121.9, 119.7, 118.8, 118.6, 116.9, 114.4, 113.8, 113.1,
111.1, 55.5, 34.0, 19.0; IR (KBr) νmax 3350, 3055, 2919, 2845, 1625,
1497, 1285, 1227, 1143, 1089, 744, 622 cm−1; HRMS (ESI) calcd for
C25H21NO4SNa (M + Na) 454.1089, found 454.1080.
5-Methoxy-3-(2-methyl-3-tosyl-4H-chromen-4-yl)-1H-indole
(17b). Pale yellow solid (123 mg, 92%): Rf = 0.5 (40% ethyl acetate in
1
hexanes); mp 190−192 °C; H NMR (400 MHz, CDCl3) δ 7.86 (s,
1H), 7.14−7.07 (m, 6H), 7.02−6.96 (m, 2H), 6.80 (d, J = 7.7 Hz,
2H), 6.71−6.68 (m, 2H), 5.48 (s, 1H), 3.70 (s, 3H), 2.49 (s, 3H), 2.19
(s, 3H); 13C NMR (100 MHz, CDCl3) δ 158.9, 153.9, 149.1, 142.7,
139.2, 131.5, 129.2, 128.6, 127.7, 126.4, 125.8, 125.0, 124.2, 123.4,
118.8, 115.8, 112.0, 111.7, 100.6, 55.6, 33.5, 21.3, 18.9; IR (KBr) νmax
3340, 2922, 1639, 1485, 1453, 1297, 1234, 1144, 1087, 1039, 751, 667
cm−1; HRMS (ESI) calcd for C26H23NO4SNa (M + Na) 468.1245,
found 468.1240.
5-Bromo-3-[2-methyl-3-(phenylsulfonyl)-4H-chromen-4-yl]-1H-
indole (18a). Yellow solid (137 mg, 95%): Rf = 0.4 (40% ethyl acetate
in hexanes); mp 188−190 °C; 1H NMR (500 MHz, CDCl3) δ 8.04 (s,
1H), 7.33−7.31 (m, 3H), 7.21 (t, J = 7.3 Hz, 1H), 7.16−7.09 (m, 3H),
7.07−7.02 (m, 5H), 6.98 (dt, J = 1.2, 7.6 Hz, 1H), 5.46 (s, 1H), 2.56
(s, 3H); 13C NMR (75 MHz, CDCl3) δ 159.5, 148.7, 141.9, 134.9,
132.1, 128.9, 128.1, 127.9, 126.9, 126.3, 125.0, 124.7, 124.0, 123.8,
121.1, 118.7, 116.2, 115.2, 112.9, 112.7, 33.4, 19.0; IR (KBr) νmax
3331, 3661, 2922, 1638, 1451, 1322, 1289, 1231, 1140, 1087, 764, 721,
628 cm−1; HRMS (ESI) calcd for C24H18BrNO3SNa (M + Na)
502.0088, found 502.0010.
3-(6-Bromo-2-methyl-3-tosyl-4H-chromen-4-yl)-1H-indole (22).
Pale yellow solid (105 mg, 71%): Rf = 0.6 (40% ethyl acetate in
1
hexanes); mp 160−162 °C; H NMR (400 MHz, CDCl3) δ 8.00 (s,
1H), 7.22−7.19 (m, 3H), 7.16 (d, J = 8.0 Hz, 1H), 7.12−7.04 (m,
4H), 6.91−6.88 (m, 2H), 6.76 (d, J = 8.1 Hz, 2H), 5.45 (s, 1H), 2.51
(s, 3H), 2.17 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 158.7, 148.0,
142.8, 138.9, 136.4, 131.8, 130.7, 128.6, 126.4, 126.3, 125.2, 122.9,
122.0, 119.8, 118.4, 118.3, 117.8, 117.1, 115.8, 111.2, 33.5, 21.3, 18.9;
IR (KBr) νmax 3442, 3125, 3060, 2922, 1638, 1477, 1318, 1292, 1230,
1146, 1089, 814, 741, 672 cm−1; HRMS (ESI) calcd for
C25H20BrNO3SNa (M + Na) 518.0224, found 518.0229.
5-Bromo-3-(2-methyl-3-tosyl-4H-chromen-4-yl)-1H-indole (18b).
Yellow solid (145 mg, 98%): Rf = 0.4 (40% ethyl acetate in hexanes);
mp 178−180 °C; 1H NMR (500 MHz, CDCl3) δ 8.20 (s, 1H), 7.29 (s,
1H), 7.20 (d, J = 8.2 Hz, 2H), 7.14−7.08 (m, 3H), 7.04−6.95 (m,
4H), 6.84 (d, J = 8.2 Hz, 2H), 5.42 (s, 1H), 2.55 (s, 3H), 2.19 (s, 3H);
13C NMR (75 MHz, CDCl3) δ 159.1, 148.6, 143.0, 138.8, 134.9,
128.85, 128.7, 127.8, 126.9, 126.35, 124.9, 124.5, 124.0, 123.8, 121.1,
118.6, 116.1, 115.5, 112.8, 112.6, 33.4, 21.3, 18.9; IR (KBr) νmax 3400,
2922, 1635, 1456, 1289, 1233, 1145, 1090, 752, 674 cm−1; HRMS
(ESI) calcd for C25H20BrNO3SNa (M + Na) 518.0224, found
518.0218.
2-[2-Methyl-3-(phenylsulfonyl)-4H-chromen-4-yl]-1H-pyrrole
(23a). Colorless solid (88 mg, 84%): Rf = 0.7 (40% ethyl acetate in
1
hexanes); mp 193−195 °C; H NMR (400 MHz, CDCl3) δ 8.92 (s,
1H), 7.55−7.50 (m, 3H), 7.43−7.39 (m, 2H), 7.26−7.22 (m, 1H),
7.18 (dd, J = 1.2, 7.6 Hz, 1H), 7.13−7.09 (m, 1H), 7.04 (d, J = 8.2 Hz,
1H), 6.67−6.65 (m, 1H), 6.03−6.01 (m, 1H), 5.47−5.45 (m, 1H),
5.26 (s, 1H), 2.29 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 160.6,
150.0, 142.4, 134.0, 132.8, 129.3, 129.0, 128.2, 126.6, 125.1, 122.6,
117.5, 116.1, 115.9, 108.2, 106.9, 34.9, 18.8; IR (KBr) νmax 3370, 2924,
1642, 1289, 1242, 1146, 1089, 760, 724, 629 cm−1; HRMS (ESI) calcd
for C20H17NO3SNa (M + Na) 374.0827, found 374.0834.
2-(2-Methyl-3-tosyl-4H-chromen-4-yl)-1H-pyrrole (23b). Colorless
solid (107 mg, 98%): Rf = 0.7 (40% ethyl acetate in hexanes); mp
186−188 °C; 1H NMR (500 MHz, CDCl3) δ 8.98 (s, 1H), 7.42 (d, J =
8.3 Hz, 2H), 7.26−7.17 (m, 4H), 7.12−7.09 (m, 1H), 7.03 (d, J = 8.1
Hz, 1H), 6.68−6.66 (m, 1H), 6.02 (dd, J = 2.8, 5.8 Hz, 1H), 5.44 (s,
1H), 5.23 (s, 1H), 2.38 (s, 3H), 2.28 (s, 3H); 13C NMR (75 MHz,
CDCl3) δ 160.3, 150.1, 143.8, 139.5, 134.1, 129.6, 129.3, 128.2, 126.7,
125.0, 122.7, 117.5, 116.2, 116.0, 108.1, 106.8, 34.9, 21.5, 18.7; IR
(KBr) νmax 3366, 2927, 1637, 1322, 1297, 1236, 1145, 753, 730, 667
cm−1; HRMS (ESI) calcd for C21H19NO3SNa (M + Na) 388.0983,
found 388.0984.
1-Ethyl-3-[2-methyl-3-(phenylsulfonyl)-4H-chromen-4-yl]-1H-in-
dole (19a). Pale yellow solid (127 mg, 99%): Rf = 0.7 (40% ethyl
acetate in hexanes); mp 170−172 °C; 1H NMR (500 MHz, CDCl3) δ
7.24 (d, J = 8.1 Hz, 1H), 7.21 (dd, J = 1.1, 8.4 Hz, 2H), 7.17−7.09 (m,
4H), 7.07−7.04 (m, 1H), 7.02 (dd, J = 0.9, 8.1 Hz, 1H), 6.98−6.93
(m, 4H), 6.90−6.87 (m, 1H), 5.51 (s, 1H), 3.97 (q, J = 7.3 Hz, 2H),
2.54 (s, 3H), 1.37 (t, J = 7.3 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ
159.1, 148.8, 142.2, 136.0, 131.6, 129.1, 127.7, 127.5, 126.1, 126.0,
125.6, 124.9, 124.4, 121.3, 119.1, 118.8, 117.4, 115.9, 115.6, 109.1,
40.6, 33.4, 19.0, 15.3; IR (KBr) νmax 3448, 3123, 3054, 2962, 2927,
1637, 1321, 1297, 1235, 1149, 745, 719, 628 cm−1; HRMS (ESI) calcd
for C26H23NO3SNa (M + Na) 452.1296, found 452.1291.
2-(6-Bromo-2-methyl-3-tosyl-4H-chromen-4-yl)-1H-pyrrole (24).
1-Ethyl-3-(2-methyl-3-tosyl-4H-chromen-4-yl)-1H-indole (19b).
Colorless solid (132 mg, 99%): Rf = 0.7 (40% ethyl acetate in
hexanes); mp 144−146 °C; 1H NMR (500 MHz, CDCl3) δ 7.24 (d, J
= 7.9 Hz, 1H), 7.14−7.04 (m, 6H), 7.01 (dd, J = 1.1, 8.2 Hz, 1H),
6.97−6.93 (m, 2H), 6.89 (dt, J = 0.9, 7.9 Hz, 1H), 6.73 (d, J = 8.1 Hz,
Colorless solid (130 mg, 98%): Rf = 0.7 (40% ethyl acetate in
1
hexanes); mp 191−193 °C; H NMR (300 MHz, CDCl3) δ 8.98 (s,
1H), 7.40 (d, J = 8.1 Hz, 2H), 7.35−7.31 (m, 2H), 7.22 (d, J = 8.1 Hz,
2H), 6.92 (d, J = 8.5 Hz, 1H), 6.69 (s, 1H), 6.05−6.04 (m, 1H), 5.47
(s, 1H), 5.18 (s, 1H), 2.39 (s, 3H), 2.28 (s, 3H); 13C NMR (125 MHz,
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J. Org. Chem. XXXX, XXX, XXX−XXX