3066
T.H.H. Hsieh, V.M. Dong / Tetrahedron 65 (2009) 3062–3068
NMR (100 MHz, CDCl3)
d
137.1, 135.4, 132.7, 132.1, 129.4, 127.2, 123.6,
(100 MHz, CDCl3) d 159.9, 146.2, 137.1, 129.7, 127.2, 126.9, 121.4,
121.9, 120.8, 119.4, 118.0, 111.3, 21.6, 21.1; LRMS (EI) m/z 221 (M);
HRMS (EI) exact mass calcd for (C16H15N) requires m/z 221.1204,
found m/z 221.1199.
120.7, 119.9, 118.6, 113.0, 112.5, 111.4, 102.1, 55.3, 55.2; LRMS (EI) m/z
253 (M); HRMS (EI) exact mass calcd for (C16H15NO2) requires m/z
253.1103, found m/z 253.1093.
4.3.3. 6-tert-Butyl-3-(4-tert-butylphenyl)indole (8c)
4.3.7. 5-Chloro-3-(3-chlorophenyl)indole (8g)
Prepared according to the general procedure for 8 from 2,2-di(4-
tert-butylphenyl)-1-nitroethylene (0.101 g, 0.30 mmol), Pd(OAc)2
(1.38 mg, 0.006 mmol), phen (2.24 mg, 0.012 mmol), and DMF
(1.5 mL) to provide the title compound as an off-white solid
(83.5 mg, 0.27 mmol) in 91% yield: mp 174–175 ꢀC; IR (neat) 3423,
3379, 3109, 3080, 3032, 2949, 2900, 2862, 1610, 1546, 1456, 1386,
1359, 1269, 1246, 1197, 1101, 962, 854, 839, 796, 786, 702 cmꢁ1; 1H
Prepared according to the general procedure for 8 from 2,2-di(3-
chlorophenyl)-1-nitroethylene (89.0 mg, 0.30 mmol), Pd(OAc)2
(1.38 mg, 0.006 mmol), phen (2.24 mg, 0.012 mmol), and DMF
(1.5 mL) to provide the title compound as a light-brown oil
(31.9 mg, 0.12 mmol) in 40% yield: IR (neat) 3435, 3118, 3062, 2924,
2852, 1597, 1571, 1541, 1460, 1398, 1342, 1286, 1238, 1095, 989, 891,
796, 781 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d 8.29 (br s, 1H, NH), 7.87
NMR (400 MHz, CDCl3)
d
8.01 (br s, 1H, NH), 7.95 (d, J¼8.6 Hz, 1H),
(d, J¼2.0 Hz, 1H), 7.58 (t, J¼1.8 Hz, 1H), 7.50 (dt, J¼7.7 and 2.8 Hz,
7.68 (d, J¼8.2 Hz, 2H), 7.54 (d, J¼8.3 Hz, 2H), 7.44 (s, 1H), 7.34 (d,
1H), 7.40–7.33 (m, 3H), 7.30–7.27 (m,1H), 7.22 (dd, J¼8.7 and 2.0 Hz,
J¼8.5 Hz, 1H), 7.29 (d, J¼2.4 Hz, 1H), 1.47 (s, 9H), 1.45 (s, 9H); 13C
1H); 13C NMR (100 MHz, CDCl3)
d 136.6, 134.9, 134.6, 130.0, 127.2,
NMR (100 MHz, CDCl3)
d
148.6, 145.7, 136.8, 132.9, 126.9, 125.6,
126.5, 126.4, 126.2, 125.4, 123.4, 123.0, 119.0, 116.8, 112.5; LRMS (EI)
m/z 261 (M); HRMS (EI) exact mass calcd for (C14H9Cl2N) requires
m/z 261.0112, found m/z 261.0110.
123.5, 121.3, 119.4, 118.5, 117.8, 107.6, 34.7, 34.5, 31.8, 31.4; LRMS (EI)
m/z 305 (M); HRMS (EI) exact mass calcd for (C22H27N) requires m/z
305.2144, found m/z 305.2136.
4.3.8. 7-Chloro-3-(3-chlorophenyl)indole (8h)
4.3.4. 6-Methoxy-3-(4-methoxyphenyl)indole (8d)
Prepared according to the general procedure for 8 from
Prepared according to the general procedure for 8 from 2,2-di(4-
methoxyphenyl)-1-nitroethylene (85.7 mg, 0.30 mmol), Pd(OAc)2
(1.38 mg, 0.006 mmol), phen (2.24 mg, 0.012 mmol), and DMF
(1.5 mL) to provide the title compound as an off-white solid
(72.7 mg, 0.29 mmol) in 93% yield: mp 144–145 ꢀC; IR (neat) 3412,
3012, 2953, 2929, 2904, 2837, 2360, 1735, 1627, 1543, 1498, 1450,
1438, 1390, 1334, 1311, 1288, 1265, 1182, 1163, 1151, 1114, 1103, 1028,
2,2-di(3-chlorophenyl)-1-nitroethylene (89.0 mg, 0.30 mmol),
Pd(OAc)2 (1.38 mg, 0.006 mmol), phen (2.24 mg, 0.012 mmol),
and DMF (1.5 mL) to provide the title compound as an off-white
solid (42.4 mg, 0.16 mmol) in 51% yield: mp 95–97 ꢀC; IR (neat)
3414, 3390, 3120, 3072, 2926, 2854, 2358, 1589, 1570, 1554, 1537,
1490, 1469, 1433, 1390, 1342, 1298, 1269, 1249, 1211, 1170, 1134,
1111, 1080, 1051, 997, 891, 877, 837, 819, 783, 761, 734 cmꢁ1
NMR (300 MHz, CDCl3)
;
1H
956, 827, 788, 748, 719, 705 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
8.03
d
8.51 (br s, 1H, NH), 7.81 (d, J¼7.9 Hz,
(br s, 1H, NH), 7.80 (d, J¼8.7 Hz, 1H), 7.60 (d, J¼8.7 Hz, 2H), 7.15 (d,
J¼2.4 Hz, 1H), 7.03 (d, J¼8.7 Hz, 2H), 6.89 (dd, J¼8.7 and 2.3 Hz, 1H),
6.85 (d, J¼2.2 Hz, 1H), 3.88 (s, 3H), 3.86 (s, 3H); 13C NMR (100 MHz,
1H), 7.64 (s, 1H), 7.53 (d, J¼7.8 Hz, 1H), 7.42–7.35 (m, 2H), 7.30–
7.27 (m, 2H), 7.16 (t, J¼7.8 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d
136.8, 134.6, 133.9, 130.0, 127.3, 126.8, 126.3, 125.5, 122.6, 122.0,
CDCl3)
d
158.0, 156.5, 137.3, 128.3, 128.2, 120.3, 120.2, 119.9, 117.7,
121.3, 118.2, 118.1, 116.9; LRMS (EI) m/z 261 (M); HRMS (EI) exact
mass calcd for (C14H9Cl2N) requires m/z 261.0112, found m/z
261.0101.
114.2,110.1, 94.7, 55.6, 55.3; LRMS (EI) m/z 253 (M); HRMS (EI) exact
mass calcd for (C16H15NO2) requires m/z 253.1103, found m/z
253.1101.
4.3.9. 6-Chloro-3-(4-chlorophenyl)indole (8i)
4.3.5. 5-Methoxy-3-(3-methoxyphenyl)indole (8e)
Prepared according to the general procedure for 8 from 2,2-di(4-
chlorophenyl)-1-nitroethylene (88.2 mg, 0.30 mmol), Pd(OAc)2
(1.38 mg, 0.006 mmol), phen (2.24 mg, 0.012 mmol), and DMF
(1.5 mL) to provide the title compound as an off-white solid
(77.7 mg, 0.30 mmol) in 98% yield: mp 142–144 ꢀC; IR (neat) 3435,
3064, 2922, 2852, 1595, 1539, 1485, 1452, 1444, 1413, 1382, 1327,
1290, 1255, 1222, 1147, 1107, 1087, 1062, 1008, 958, 900, 837, 812,
Prepared according to the general procedure for 8 from 2,2-di(3-
methoxyphenyl)-1-nitroethylene (84.6 mg, 0.30 mmol), Pd(OAc)2
(1.38 mg, 0.006 mmol), phen (2.24 mg, 0.012 mmol), and DMF
(1.5 mL) to provide the title compound as a light-brown oil
(35.0 mg, 0.14 mmol) in 43% yield: IR (neat) 3406, 2993, 2933, 2904,
2829,1600,1583,1541,1477,1454,1436,1411,1321,1298,1278,1215,
1172, 1111, 1033, 987, 921, 840, 794, 783 cmꢁ1
;
1H NMR (400 MHz,
798, 785, 742, 713 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d 8.18 (br s, 1H,
CDCl3) 8.15 (br s, 1H, NH), 7.42–7.35 (m, 2H), 7.31 (m, 1H), 7.27 (d,
d
NH), 7.77 (d, J¼8.6 Hz, 1H), 7.55 (d, J¼8.5 Hz, 2H), 7.42–7.39 (m, 3H),
J¼5.4 Hz, 1H), 7.24 (s, 1H), 7.21 (s, 1H), 6.92 (dd, J¼8.8 and 2.4 Hz,
7.33 (d, J¼2.6 Hz, 1H), 7.18 (dd, J¼8.6 and 1.8 Hz, 1H); 13C NMR
1H), 6.86 (dd, J¼8.2 and 2.5 Hz, 1H), 3.88 (s, 3H), 3.87 (s, 3H); 13C
(100 MHz, CDCl3)
d 136.9, 133.4, 131.9, 128.9, 128.5, 128.4, 124.1,
NMR (100 MHz, CDCl3)
d
159.9, 154.7, 137.1, 131.7, 129.8, 126.1, 122.7,
122.3, 121.2, 120.4, 117.3, 111.4; LRMS (EI) m/z 261 (M); HRMS (EI)
exact mass calcd for (C14H19Cl2N) requires m/z 261.0112, found m/z
261.0103.
119.9, 117.9, 113.0, 112.7, 112.1, 111.3, 101.6, 55.9, 55.2; LRMS (EI) m/z
253 (M); HRMS (EI) exact mass calcd for (C16H15NO2) requires m/z
253.1103, found m/z 253.1091.
4.3.10. 5-Trifluoromethyl-3-(3-trifluoromethylphenyl)indole (8j)
Prepared according to the general procedure for 8 from 2,2-
di(3-trifluoromethylphenyl)-1-nitroethylene (0.108 g, 0.30 mmol),
Pd(OAc)2 (1.38 mg, 0.006 mmol), phen (2.24 mg, 0.012 mmol),
and DMF (1.5 mL) to provide the title compound as an off-white
solid (47.0 mg, 0.14 mmol) in 45% yield: mp 75–77 ꢀC; IR (neat)
3485, 2922, 1612, 1543, 1481, 1425, 1317, 1292, 1271, 1259, 1242,
1155, 1143, 1087, 1070, 1055, 999, 981, 943, 898, 877, 810, 796,
4.3.6. 7-Methoxy-3-(3-methoxyphenyl)indole (8f)
Prepared according to the general procedure for 8 from 2,2-di(3-
methoxyphenyl)-1-nitroethylene (84.6 mg, 0.30 mmol), Pd(OAc)2
(1.38 mg, 0.006 mmol), phen (2.24 mg, 0.012 mmol), and DMF
(1.5 mL) to provide the title compound as a pink solid (39.2 mg,
0.16 mmol) in 48% yield: mp 72–74 ꢀC; IR (neat) 3404, 2966, 2933,
2854, 1625, 1604, 1577, 1498, 1477, 1444, 1431, 1413, 1369, 1346,
1332, 1265, 1249, 1220, 1168, 1149, 1101, 1091, 1074, 1058, 1037, 989,
777, 756, 707 cmꢁ1 1H NMR (400 MHz, CDCl3)
; d 8.49 (br s, 1H,
925, 873, 815, 777, 738 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
8.48 (br s,
NH), 8.16 (s, 1H), 7.87–7.82 (m, 2H), 7.66–7.58 (m, 2H), 7.53 (s,
1H, NH), 7.58 (d, J¼8.2 Hz, 1H), 7.40–7.34 (m, 2H), 7.29 (d, J¼7.6 Hz,
1H), 7.25 (s, 1H), 7.13 (t, J¼7.9 Hz, 1H), 6.86 (dd, J¼8.2 and 2.5 Hz,
1H), 6.72 (d, J¼7.7 Hz, 1H), 3.99 (s, 3H), 3.89 (s, 3H); 13C NMR
2H), 7.51 (d, J¼2.6 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d 137.9,
135.3, 131.3 (q, J¼32.2 and 32.2 Hz, CF3), 130.7, 129.4, 126.5,
125.6, 124.9, 124.2 (q, J¼3.9 and 3.8 Hz), 123.8, 123.2 (q, J¼31.9