Palladium-Catalyzed Cross-Coupling of 1-Aminoazoles with Aryl Chlorides
CDCl3): d=7.74–7.59 (m, 1H), 7.35–7.02 (m, 6H), 6.61 (s,
1H), 6.55 (dd, J=3.4, 0.7 Hz, 1H), 6.44 (d, J=8.9 Hz, 2H);
13C NMR (75 MHz, CDCl3): d=146.08 (C), 135.77 (C),
129.48 (2CH), 128.56 (CH), 126.83 (C), 126.14 (C), 122.74
(CH), 121.36 (CH), 120.70 (CH), 114.08 (2CH), 109.43
(CH), 101.29 (CH); MS (APCI negative): m/z=241
[MÀH]À; HR-MS (APCI negative): m/z=241.0525, calcd.
for C14H11ClN2 (MÀH): 241.0527.
121.58 (C), 121.08 (CH), 111.89 (CH), 110.94 (d, J=
26.4 Hz), 110.18 (d, J=9.7 Hz), 106.08 (d, J=23.7 Hz),
100.82 (d, J=4.4 Hz), 17.19 (CH3); 19F NMR (188 MHz,
CDCl3): d=À122.3 (s); MS (APCI positive): m/z=241 [M+
H]+; HR-MS (APCI positive): m/z=241.1143, calcd. for
C15H13FN2 (M+H): 241.1136.
N-(3,5-Dimethoxyphenyl)-3-methyl-1H-indol-1-amine
(3m): Yield: 48% (46 mg), white-yellow oil, Rf =0.30 (cyclo-
hexane/EtOAc 9:1); IR (neat): n=3489, 3342, 2837, 2162,
2059, 2021, 1621, 1596, 1509, 1478, 1459, 1416, 1343, 1309,
Ethyl 4-[(1H-indol-1-yl)amino]benzoate (3i): Yield: 55%
(60 mg), white-yellow solid, mp 165–1678C, Rf =0.50 (cyclo-
hexane/EtOAc 8:2); IR (neat): n=3469, 3421, 3368, 3184,
3105, 2357, 2211, 2016, 1964, 1713, 1688, 1605, 1511, 1367,
1229, 1204, 1149, 1111, 1068, 1059, 11010, 993 cmÀ1
;
1H NMR (300 MHz, CDCl3): d=7.58 (d, J=7.0 Hz, 1H),
7.42–7.04 (m, 3H), 6.93 (s, 1H), 6.49 (s, 1H), 6.03 (s, 1H),
5.72 (d, J=2.0 Hz, 2H), 3.68 (s, 6H), 2.34 (s, 3H); 13C NMR
(75 MHz, CDCl3): d=161.91 (2C), 149.90 (C), 136.54 (C),
127.05 (C), 126.06 (CH), 122.53 (CH), 119.80 (CH), 119.10
(CH), 110.31 (C), 109.33 (CH), 92.93 (CH), 91.70 (CH),
55.38 (2OMe), 9.77 (CH3); MS (ESI positive): m/z=283
[M+H]+; HR-MS (ESI positive): m/z=283.1448, calcd. for
C17H18N2O2 (M+H): 283.1447.
1
1278, 1254, 1217, 1172, 1106, 766 cmÀ1; H NMR (300 MHz,
CDCl3): d=7.89 (d, J=8.8 Hz, 2H), 7.72–7.59 (m, 1H),
7.24–7.13 (m, 4H), 6.92 (s, NH), 6.57 (d, J=3.2 Hz, 1H),
6.49 (d, J=8.8 Hz, 2H), 4.32 (q, J=7.1 Hz, 2H), 1.35 (t, J=
7.1 Hz, 3H); 13C NMR (75 MHz, CDCl3): d=166.31 (C),
151.05 (C), 135.57 (C), 131.45 (2CH), 128.35 (CH), 126.64
(C), 123.01 (C), 122.70 (CH), 121.24 (CH), 120.67 (CH),
111.63 (2CH), 109.20 (CH), 101.41 (CH), 60.58 (CH2), 14.35
(CH3); MS (ESI positive): m/z=281 [M+H]+; HR-MS
(ESI): m/z=281.1290, calcd. for C17H16N2O2 (M+H):
281.1299.
5-Chloro-N-(naphthalen-1-yl)-1H-indol-1-amine
(3n):
Yield: 63% (60 mg), white-yellow oil, Rf =0.47 (cyclohex-
ane/EtOAc 9:1) ; IR (neat): n=3471, 3449, 3418, 3347, 3256,
3233, 3075, 2361, 2246, 2216, 2189, 2163, 2072, 2043, 2024,
1598, 1581, 1526, 1507, 1481, 1457, 1403, 1271, 1205, 1153,
5-Methoxy-N-(4-methoxyphenyl)-1H-indol-1-amine (3j):
Yield: 61% (50 mg), white-yellow solid, mp 74–768C, Rf =
0.43 (cyclohexane/EtOAc 8:2); IR (neat): n=3312, 3240,
2833, 2363, 2180, 2001, 1622, 1587, 1509, 1489, 1469, 1433,
1325, 1287, 1243, 1229, 1210, 1180, 1147, 1090, 1031, 937,
1
1093, 1058, 905 cmÀ1; H NMR (300 MHz, CDCl3): d=8.05–
7.83 (m, 2H), 7.67 (d, J=1.8 Hz, 1H), 7.63–7.51 (m, 2H),
7.45 (d, J=8.2 Hz, 1H), 7.28 (d, J=3.3 Hz, 1H), 7.24–7.09
(m, 4H), 6.56 (dd, J=3.3, 0.7 Hz, 1H), 6.08 (d, J=7.6 Hz,
1H); 13C NMR (75 MHz, CDCl3): d=141.80 (C), 134.29 (C),
134.22 (C), 130.09 (CH), 129.04 (CH), 127.74 (C), 126.41
(CH), 126.28 (CH), 126.01 (CH), 123.02 (CH), 122.28 (C),
121.72 (CH), 120.77 (CH), 119.53 (CH), 110.61 (CH), 107.44
(CH), 100.87 (CH); MS (ESI positive): m/z=293 [M+H]+;
HR-MS (APCI positive): m/z=293.0814, calcd. for
C18H13ClN2 (M+H): 293.0820.
823, 800 cmÀ1 1H NMR (300 MHz, CDCl3): d=7.17 (m,
;
2H), 7.11 (d, J=2.3 Hz, 1H), 6.84 (dd, J=9.0, 2.3 Hz, 1H),
6.76 (d, J=9.0 Hz, 2H), 6.52–6.42 (m, 4H), 3.86 (s, 3H),
3.74 (s, 3H); 13C NMR (75 MHz, CDCl3): d=154.59 (C),
154.52 (C), 141.19 (C), 130.98 (C), 129.20 (CH), 127.04 (C),
114.75 (2CH), 114.18 (2CH), 112.54 (CH), 110.26 (CH),
102.78 (CH), 100.03 (CH), 55.82 (OMe), 55.61 (OMe); MS
(APCI positive): m/z=269 [M+H]+; HR-MS (APCI):
m/z=269.1279, calcd. for C16H16N2O2 (M+H): 269.1285.
N-(2-Chlorophenyl)-5-methoxy-1H-indol-1-amine
(3o):
N-(4-Methoxyphenyl)-3-methyl-1H-indol-1-amine
(3k):
Yield: 70% (59 mg), white-yellow oil, Rf =0.69 (cyclohex-
ane/EtOAc 8:2); IR (neat): n=3423, 3337, 2832, 2361, 2163,
2145, 2013, 1961, 1623, 1595, 1494, 1476, 1442, 1385, 1362,
1343, 1301, 1284, 1251, 1229, 1202, 1146, 1127, 1089, 1053,
Yield: 70% (59 mg), white-yellow solid, mp 115–1178C, Rf =
0.33 (cyclohexane/EtOAc 9:1); IR (neat): n=3429, 2338,
2321, 2246, 2207, 2164, 2060, 2043, 2023, 1984, 1941, 1510,
1453, 1237, 1180, 1033, 824, 741, 703 cmÀ1
;
1H NMR
1032, 936 cmÀ1; H NMR (300 MHz, CDCl3): d=7.35 (d, J=
1
(300 MHz, CDCl3): d=7.60 (dd, J=6.5, 1.7 Hz, 1H), 7.29–
7.24 (m, 1H), 7.22–7.10 (m, 2H), 6.96 (d, J=0.9 Hz, 1H),
6.76 (d, J=8.9 Hz, 2H), 6.50 (d, J=8.9 Hz, 2H), 6.40 (s,
NH), 3.74 (s, 3H), 2.35 (s, 3H); 13C NMR (75 MHz, CDCl3):
d=154.64 (C), 141.52 (C), 136.49 (C), 127.10 (C), 126.10
(CH), 122.43 (CH), 119.71 (CH), 119.12 (CH), 114.91
(2CH), 114.38 (2CH), 110.09 (C), 109.44 (CH), 55.78
(OMe), 9.75 (CH3); MS (ESI positive): m/z=253 [M+H]+;
HR-MS (ESI): m/z=253.1347, calcd. for C16H16N2O (M+
H)+: 253.1341.
7.9 Hz, 1H), 7.21–7.08 (m, 4H), 7.00 (t, J=7.8 Hz, 1H),
6.92–6.75 (m, 2H), 6.49 (d, J=3.2 Hz, 1H), 6.10 (d, J=
8.1 Hz, 1H), 3.86 (s, 3H); 13C NMR (75 MHz, CDCl3): d=
154.82 (C), 143.26 (C), 130.69 (C), 129.31 (CH), 129.10
(CH), 128.03 (CH), 127.12 (C), 121.37 (CH), 117.89 (C),
113.47 (CH), 112.83 (CH), 109.98 (CH), 102.90 (CH), 100.74
(CH), 55.81 (OMe); MS (ESI positive): m/z=273 [M+H]+;
HR-MS (ESI positive): m/z=273.0806, calcd. for
C15H13ClN2O (M+H): 273.0795.
N-(2-Chlorophenyl)-1H-benzo[d]imidazol-1-amine
5-Fluoro-N-(o-tolyl)-1H-indol-1-amine (3l): Yield: 48%
(46 mg), orange oil, Rf =0.46 (cyclohexane/EtOAc 9:1); IR
(neat): n=3361, 2174, 2040, 1589, 1501, 1469, 1442, 1364,
(3p):Yield: 50% (45 mg), white-yellow oil, Rf =0.54 (EtOAc
100%); IR (neat): n=3419, 3398, 3351, 2365, 2242, 2174,
2025, 1606, 1510, 1478, 1450, 1306, 1277, 1236, 1204, 1175,
1
1335, 1300, 1274, 1229, 1124, 1047, 945, 863 cmÀ1; H NMR
1119, 1071, 1032, 1002 cmÀ1 1H NMR (300 MHz, CDCl3):
;
(300 MHz, CDCl3): d=7.43 (dd, J=9.4, 2.3 Hz, 1H), (dd,
7.32 (dd, J=9.4, 2.3 Hz, 1H), 7.25 (d, J=3.3 Hz, 1H), 7.23–
7.10 (m, 2H), 7.05–6.92 (m, 2H), 6.95–6.78 (m, 2H), 6.53 (d,
J=3.4 Hz, 1H), 2.37 (s, 3H); 13C NMR (75 MHz, CDCl3):
d=158.45 (C) (d, J=234.9 Hz), 145.0 (C), 132.49 (C), 130.69
(CH), 130.44 (CH), 127.43 (CH), 126.88 (d, J=10.3 Hz),
d=8.05 (s, 1H), 7.82 (d, J=7.6 Hz, 1H), 7.38–7.22 (m, 3H),
6.78 (d, J=9.0 Hz, 2H), 6.78 (s, NH), 6.58 (d, J=9.0 Hz,
2H), 3.74 (s, 3H); 13C NMR (75 MHz, CDCl3): d=155.36
(C), 142.12 (C), 139.71 (C), 133.22 (C), 123.80 (CH), 122.96
(CH), 120.94 (CH), 115.02 (5CH), 109.90 (CH), 55.74
(CH3); MS (ESI positive): m/z=240 [M+H]+; HR-MS (ESI
Adv. Synth. Catal. 2012, 354, 2829 – 2839
ꢂ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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