1 Supporting Information Gold-catalyzed Synthesis of 3-arylindoles via Annulation of Nitrosoarenes and Alkynes Siva Murru, August A. Gallo and Radhey S. Srivastava* Department of Chemistry, University of Louisiana at Lafayette, Lafayette, LA 70504 List of Contents 1. General Information 1 2. Spectral data for all compounds 2-6 3. Spectra ( 1 H NMR and 13 C NMR) of all compounds 7-30 General information: All the reagents were commercial grade and purified according to the established procedures. Nitrosoarenes 1-9 were prepared from their corresponding anilines by using catalytic hydrogen peroxide oxidation procedure. 1 Organic extracts were dried over anhydrous sodium sulphate. Solvents were removed in a rotary evaporator under reduced pressure. Silica gel (60-120 mesh size) was used for the column chromatography. Reactions were monitored by TLC on aluminum backed silica G TLC plates w/uv254. NMR spectra were recorded in CDCl 3 with tetramethylsilane (TMS) as the internal standard for 1 H NMR (400 MHz). CDCl 3 solvent as the internal standard for 13 C NMR (100 MHz). General Procedure for the Preperation of Nitrosoarenes: To the solution of substituted aniline (5 mmol), Diphenyl diselenide (0.25 mmol, 5 mol%) in chloroform (5 ml), was added aq. H 2 O 2 (30 % w/w) ( 800 µl) and kept for stirring at room temperature. After completion of the reaction (usually 2-3 hrs), solvent was evaporated using rotavap to get the crude product and further purification was achieved using column chromatography.
2 Spectroscopic data for all the compounds: 1 H and 13 C NMR data is comparable to the known (cited below) reported compounds. 2. Spectral Data N H 3-phenyl-1H-indole (1a). 2,3,4 1 H NMR (400 MHz, CDCl 3 ): δ 7.04-7.21 (m, 4H), 7.23 (d, 1H, J = 7.8 Hz), 7.35 (t, 2H, J = 7.6 Hz), 7.58 (d, 2H, J = 7.8 Hz), 7.84 (d, 1H, J = 7.6 Hz), 8.06 (brs, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 110.4, 117.1, 118.7, 119.214, 120.8, 121.3, 124.6, 124.9, 126.4, 127.7, 134.5, 135.5; IR (KBr): 3417, 3056, 2964, 1671, 1601, 1574, 1455, 1336, 1257, 1173, 1098, 959 cm -1. ------------------------------------------------------------------------------------------------------------------------------------------ Me N H 5-methyl-3-phenyl-1H-indole (2a). 2,3 1 H NMR (400 MHz, CDCl 3 ): δ 2.46 (s, 3H), 7.04 (d, 1H, J = 8.0 Hz), 7.23 (brs, 2H), 7.42 (t, 3H, J = 7.55 Hz), 7.64 (d, 2H, J = 7.30 Hz), 7.71 (s, 1H), 8.22 (brs, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 21.9, 111.4, 117.8, 119.6, 122.3, 124.1, 126.0, 127.7, 128.9, 129.7, 131.1, 135.2, 136.0; IR (KBr): 3411, 3025, 2920, 2860, 1600, 1492, 1447, 1416, 1261, 1216, 1108, 1027, 798, 765, 699, 588 cm -1. ------------------------------------------------------------------------------------------------------------------------------------------ MeO N H 5-methoxy-3-phenyl-1H-indole (3a). 6 1 H NMR (400 MHz, CDCl 3 ): δ 3.81 (s, 3H), 6.88 (d, 1H, J = 8.7 Hz), 7.15 7.16 (m, 2H), 7.25 (t, 1H, J = 7.4 Hz), 7.38 7.43 (m, 3H), 7.61 (d, 2H, J =
3 7.1 Hz), 8.10 (brs, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 56.3, 101.9, 112.6, 112.8, 118.0, 123.2, 126.1, 126.3, 127.6, 129.2, 132.2, 136.1, 154.9; IR (KBr): 3417, 2998, 2938, 2830, 1621, 1601, 1552, 1479, 1294, 1269, 1114, 1032, 916, 800, 764 cm -1. ------------------------------------------------------------------------------------------------------------------------------------------ Cl N H 5-chloro-3-phenyl-1H-indole (4a). 2,4,5 1 H NMR (400 MHz, CDCl 3 ): δ 7.15 (d, 1H, J = 8.6 Hz), 7.23 7.29 (m, 3H), 7.42 (t, 2H, J = 7.6 Hz), 7.58 (d, 2H, J = 7.6 Hz), 7.87 (s, 1H), 8.19 (brs, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 112.7, 118.3, 119.4, 122.9, 123.3, 126.3, 126.5, 127.0, 127.6, 129.1, 135.0, 135.2; IR (KBr): 3423, 3058, 3030, 2924, 1602, 1575, 1489, 1461, 1412, 1289, 1101, 1064, 890, 798, 762, 699 cm -1. ------------------------------------------------------------------------------------------------------------------------------------------ Br N H 5-bromo-3-phenyl-1H-indole (5a). 6 1 H NMR (400 MHz, CDCl 3 ): δ 7.18 (d, 1H, J = 8.6 Hz), 7.23 7.29 (m, 3H), 7.41 (t, 2H, J = 7.8 Hz), 7.56 (d, 2H, J = 7.22 Hz), 8.02 (s, 1H), 8.31 (brs, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 113.2, 113.8, 118.1, 122.5, 123.2, 125.4, 126.5, 127.6, 129.1, 132.3, 135.0, 135.5; IR (KBr): 3419, 3059, 3027, 2963, 2924, 1681, 1600, 1543, 1488, 1455, 1288, 1260, 1100, 883, 797, 761 cm -1. ------------------------------------------------------------------------------------------------------------------------------------------ Et 2 N N H N,N-diethyl-3-phenyl-1H-indol-5-amine (6a). 5 1 H NMR (400 MHz, CDCl 3 ): δ 1.10 (t, 6H, J = 7.0 Hz), 3.29 (q, 4H, J = 7.0 Hz), 6.91 (d, 1H, J = 8.6 Hz), 7.23 7.29 (m, 3H), 7.33 (s, 1H),
4 7.42 (t, 2H, J = 7.6 Hz), 7.63 (d, 2H, J = 7.4 Hz), 8.15 (brs, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 12.6, 46.7, 106.5, 111.9, 114.9, 117.8, 122.4, 125.8, 126.6, 127.5, 128.9, 131.4, 136.2, 143.6; IR (KBr): 3398, 2968, 2921, 1601, 1491, 1374, 1354, 1196, 796, 761, 690 cm -1. ------------------------------------------------------------------------------------------------------------------------------------------ Br N H 7-bromo-3-phenyl-1H-indole (7a). 1 H NMR (400 MHz, CDCl 3 ): δ 7.06 (t, 1H, J = 7.76 Hz), 7.30 ( t, 1H, J = 7.41 Hz), 7.38 7.40 (m, 2H), 7.44 (t, 2H, J = 7.6 Hz), 7.62 (d, 2H, J = 7.56 Hz), 7.85 (d, 1H, J = 7.9 Hz), 8.43 (brs, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 119.3, 119.8, 121.6, 122.4, 124.9, 126.5, 127.1, 127.7, 129.0, 132.4, 135.2, 135.5; IR (KBr): 3419, 3060, 2962, 2923, 2851, 1671, 1579, 1556, 1488, 1433, 1321, 1273, 1117, 1026, 779, 757 cm -1. ------------------------------------------------------------------------------------------------------------------------------------------ Me N H Me 2,7-dimethyl-3-phenyl-1H-indole (8b). 3 1 H NMR (400 MHz, CDCl 3 ): δ 2.51 (s, 3H), 2.53 (s, 3H), 6.97 (d, 1H, J = 7.0 Hz), 7.04 (t, 1H, J = 7.3 Hz), 7.25 (s, 1H), 7.29 (t, 1H, J = 7.3 Hz), 7.45 (t, 2H, J = 7.4 Hz), 7.51 (d, 2H, J = 7.8 Hz), 7.90 (brs, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 12.8, 16.8, 115.2, 116.7, 119.6, 120.3, 122.3, 125.9, 127.5, 128.6, 129.4, 129.6, 131.2, 134.8, 135.7; IR (KBr): 3417, 3053, 2922, 2855, 1714, 1601, 1597, 1455, 1300, 1261, 1083, 782, 701 cm -1. ------------------------------------------------------------------------------------------------------------------------------------------ N H Me 2-methyl-3-phenyl-1H-indole (1b). 1 H NMR (400 MHz, CDCl 3 ): δ 2.49 (s, 3H), 7.10 (t, 1H, J = 7.3 Hz), 7.16 (t, 1H, J = 7.1 Hz), 7.30 (t, 2H, J = 7.9 Hz), 7.45 (t, 2H, J = 7.6 Hz), 7.51 (d, 2H, J
5 = 7.6 Hz), 7.66 (d, 1H, J = 7.8 Hz), 7.94 (brs, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 12.7, 110.5, 114.7, 118.9, 120.1, 121.7, 126.0, 128.0, 128.7, 129.6, 131.6, 135.4, 135.6; IR (KBr): 3404, 3056, 2921, 2855, 1714, 1619, 1601, 1496, 1331, 1306, 1256, 1187, 1075, 749, 701 cm -1. ------------------------------------------------------------------------------------------------------------------------------------------ Br N H Me 5-bromo-2-methyl-3-phenyl-1H-indole (5b). 1 H NMR (400 MHz, CDCl 3 ): δ 2.44 (s, 3H), 7.13 (d, 1H, J = 8.5 Hz), 7.23 (d, 1H, J = 8.5 Hz), 7.33 7.34 (m, 1H), 7.45 7.49 (m, 4H), 7.78 (s, 1H), 8.02 (brs, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 12.7, 112.0, 113.4, 114.4, 121.5, 124.4, 126.4, 128.8, 129.5, 129.8, 133.1, 134.0, 134.9; IR (KBr): 3416, 3057, 2920, 1601, 1578, 1495, 1468, 1369, 1216, 1013, 940, 869, 795, 765 cm -1. ------------------------------------------------------------------------------------------------------------------------------------------ Me Me N H 7-methyl-3-p-tolyl-1H-indole (8c). 1 H NMR (400 MHz, CDCl 3 ): δ 2.39 (s, 3H), 2.47 (s, 3H), 7.03 (d, 1H, J = 7.0 Hz), 7.10 (t, 1H, J = 7.3 Hz), 7.24 7.27 (m, 3H), 7.55 (d, 2H, J = 8.0 Hz), 7.78 (d, 1H, J = 7.9 Hz), 8.15 (brs, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 16.6, 21.1, 117.5, 118.6, 120.3, 121.3, 122.7, 122.71, 125.2, 127.3, 127.6, 129.4, 134.9, 135.4.; IR (KBr): 3409, 3047, 2926, 2862, 2842, 1604, 1592, 1449, 1297, 1092, 784 cm -1. --------------------------------------------------------------------------------------------------------------------- EtO O N H Ethyl 3-phenyl-1H-indole-5-carboxylate (9a). 1 H NMR (400 MHz, CDCl 3 ): δ 1.33 (t, 3H, J = 7.2 Hz), 4.31 (q, 2H, J = 7.2 Hz), 7.37 (m, 6H), 7.52 (s, 2H), 7.77 (s, 1H), 8.52 (brs, 1H); 13 C
6 NMR (100 MHz, CDCl 3 ): δ 14.5, 61.2, 114.1, 119.7, 122.0, 123.0, 123.5, 126.5, 127.7, 128.8, 128.9, 129.0, 131.7, 150.9, 168.8.; IR (KBr): 3419, 3243, 2981, 1681, 1603, 1589, 1407, 1368, 1278, 1173, 1067, 868, 756 cm -1. References: 1. Zhao, D.; Johansson, M.; Backvall, J.-E. Eur. J. Org. Chem. 2007, 4431. 2. Lamar, A. A.; Nicholas, K. M. Tetrahedron 2009, 65, 3829. 3. Ragaini, F.; Rapetti, A.; Visentin, E.; Monzani, M.; Caselli, A.; Cenini, S. J. Org. Chem. 2006, 71, 3748. 4. Penoni, A.; Nicholas, K. M. Chem. Commun. 2002, 484. 5. Penoni, A.; Volkmann, J.; Nicholas, K. M. Org. Lett. 2002, 4, 699. 6. Phipps, R. J.; Grimster, N. P.; Gaunt, M. J. J. Am. Chem. Soc. 2008, 130, 8172.
7 NMR Spectras 3-phenyl-1H-indole (1a). 1 H-NMR N H 3-phenyl-1H-indole (1a). 13 C-NMR
5-methyl-3-phenyl-1H-indole (2a). 1 H-NMR 8
5-methyl-3-phenyl-1H-indole (2a). 13 C-NMR 9
5-methoxy-3-phenyl-1H-indole (3a). 1 H-NMR 10
5-methoxy-3-phenyl-1H-indole (3a). 13 C-NMR 11
5-chloro-3-phenyl-1H-indole (4a). 1 H-NMR 12
5-chloro-3-phenyl-1H-indole (4a). 13 C-NMR 13
5-bromo-3-phenyl-1H-indole (5a). 1 H-NMR 14
5-bromo-3-phenyl-1H-indole (5a). 13 C-NMR 15
16 N,N-diethyl-3-phenyl-1H-indol-5-amine (6a). 1 H-NMR
17 N,N-diethyl-3-phenyl-1H-indol-5-amine (6a). 13 C-NMR
7-bromo-3-phenyl-1H-indole (7a). 1 H-NMR 18
7-bromo-3-phenyl-1H-indole (7a). 13 C-NMR 19
20 2,7-dimethyl-3-phenyl-1H-indole (8b). 1 H-NMR
21 2,7-dimethyl-3-phenyl-1H-indole (8b). 13 C-NMR
2-methyl-3-phenyl-1H-indole (1b). 1 H-NMR 22
2-methyl-3-phenyl-1H-indole (1b). 13 C-NMR 23
24 5-bromo-2-methyl-3-phenyl-1H-indole (5b). 1 H-NMR
25 5-bromo-2-methyl-3-phenyl-1H-indole (5b). 13 C-NMR
7-methyl-3-p-tolyl-1H-indole (8c). 1 H-NMR 26
7-methyl-3-p-tolyl-1H-indole (8c). 13 C-NMR 27
28 Ethyl 3-phenyl-1H-indole-5-carboxylate (9a). 1 H-NMR
29 Ethyl 3-phenyl-1H-indole-5-carboxylate (9a). 13 C-NMR
30