Fischer Indole Synthesis in Low Melting Mixtures

Fischer Indole Synthesis in Low Melting Mixtures Sangram Gore, a,b Sundarababu Baskaran* a and Burkhard König* b Supporting Information Table of Contents: General Information General Procedure for the formation of indoles Characterization data for compounds Copy of 1 H and 13 C MR spectra of compounds S2 S2 S2-S10 S11-S127 S1

General Information 1 H MR spectra were recorded on Bruker ADVACE 400 MHz and 500 MHz spectrometers. 13 C MR spectra were recorded on 100 MHz and 125 MHz spectrometers. Chemical shifts are expressed in δ units relative to tetramethylsilane (TMS) signal as internal reference in CDCl 3. FTIR spectra were recorded in CHCl 3 or neat. Column chromatography was performed on silica gel (60-120 mesh) using ethyl acetate and hexane as eluent. General Procedure for the preparation of indole derivatives: In a typical experiment, 1.5 g of L-(+)-tartaric acid-dmu (30:70) mixture was heated to 70 o C to obtain a clear melt. To this melt, 1 mmol of aryl hydrazine.hcl and 1 mmol of aldehyde/ketone were added at 70 o C. The reaction was monitored by thin layer chromatography. After completion, the reaction mixture was quenched by adding water while still hot. The reaction mixture was cooled to room temperature and the solid that separated was filtered and washed with water (2 x 5 ml). The crude compound was dried under vacuum and recrystallized from ethanol to afford pure product. In case of liquid products, the reaction mixture was quenched with water and the aqueous layer was extracted with DCM (3 x 5 ml). The organic layer was washed with water (2 x 5 ml), dried over anhydrous a 2 SO 4 and concentrated under reduced pressure. The crude compound was purified by column chromatography over silica gel. Experimental Section Spectral data for the indole derivatives obtained by the Fischer indole reaction between aldehyde/ketone and aryl hydrazine in tartaric acid-dmu melt: 3a. 2,3,4,9-Tetrahydro-1H-carbazole: H Colorless solid; Yield 97%; M.p. 118 120 o C; IR (neat): 3396, 1455, 739 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.75 1.90 (m, 4H), 2.60 2.71 (m, 4H), 6.96 7.07 (m, 2H), 7.18 (dd, 1H, J = 7.6, 1.6 Hz) 7.38 (d, 1H, J = 7.6 Hz), 7.55 (s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 21.0, 23.3, 23.4, 110.3, 110.5, 117.8, 119.2, 121.1, 128.0, 134.2, 135.8. 3b. 5,6,7,8,9,10-Hexahydrocyclohepta[b]indole: H Colorless solid; Yield 98%; M.p. 145 147 o C; IR (neat): 3388, 1456, 741 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.72 1.81 (m, 4H), 1.85 1.93 (m, 2H), 2.80 (t, 4H, J = 5.6 Hz), 7.05 7.12 (m, 2H), 7.20 7.25 (m, 1H), 7.44 7.50 (m, 1H), 7.62 (br s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 24.8, 27.6, 28.8, 29.7, 31.9, 110.3, 113.8, 117.7, 119.1, 120.7, 129.3, 134.3, 137.5; HRMS calcd. for C 13 H 16 1 (M + +1) 186.1283, found 186.1292. S2

3c. 6,7,8,9,10,11-Hexahydro-5H-cycloocta[b]indole: H Colorless solid; Yield 96%; M.p. 73 74 o C; IR (neat): 3329, 1623, 1453, 1334, 742 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.38 1.51 (m, 4H), 1.68 1.79 (m, 4H), 2.80 2.90 (m, 4H), 7.05 7.13 (m, 2H), 7.24 7.30 (m, 1H), 7.46 7.52 (m, 1H), 7.63 (s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 22.3, 26.0, 26.1, 29.6, 29.7, 110.4, 111.8, 117.8, 119.0, 120.7, 128.7, 135.1, 135.7; HRMS calcd. for C 14 H 18 1 (M + +1) 200.1439, found 200.1432. 3d. 1,2,3,4-Tetrahydrocyclopenta[b]indole: H Colorless solid; Yield 97%; M.p. 101 103 o C; IR (neat): 3399, 1654, 1609, 1405, 1233, 741 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 2.51 2.61 (m, 2H), 2.81 2.96 (m, 4H), 7.07 7.14 (m, 2H), 7.28 7.33 (m, 1H), 7.43 7.48 (m, 1H), 7.82 (s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 24.6, 26.0, 28.8, 111.4, 118.6, 119.6, 119.9, 120.6, 124.9, 141.1, 143.8; HRMS calcd. for C 11 H 12 1 (M + +1) 158.0970, found 158.0974. 3e. 2,3-Dimethyl-1H-indole: Me H Colorless solid; Yield 88%; M.p. 104 106 o C; IR (neat): 3396, 1467, 740 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 2.12 (s, 3H), 2.20 (s, 3H), 6.95 7.05 (m, 2H), 7.06 7.12 (m, 1H), 7.33 7.44 (m, 2H); 13 C MR (100 MHz, CDCl 3 ): δ 8.5, 11.6, 107.1, 110.2, 118.0, 119.1, 121.0, 129.5, 130.8, 135.3; HRMS calcd. for C 10 H 12 1 (M + +1) 146.0970, found 146.0970. Me 3f. 3-Phenyl-1H-indole: Ph H Colorless solid; Yield 87%; M.p. 85 86 o C; IR (neat): 3405, 3048, 1597, 1451, 1111, 741, 694 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 7.17 7.32 (m, 3H), 7.33 (d, 1H, J = 2.8 Hz), 7.39 7.51 (m, 3H), 7.65 7.75 (m, 2H), 7.95 (d, 1H, J = 7.6 Hz), 8.19 (br s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 111.5, 118.5, 119.9, 120.4, 121.9, 122.5, 125.9, 126.1, 127.6, 128.9, 135.7, 136.8; HRMS calcd. for C 14 H 12 (M + +1) 194.0970, found 194.0966. S3

3g. Tert-butyl 3,4-dihydro-1H-pyrido[4,3-b]indole-2(5H)-carboxylate: Boc H Pale yellow oil; Yield 85%; IR (neat): 3317, 1686, 1405, 1152, 753 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.53 (s, 9H), 2.81 (t, 2H, J = 5.6 Hz), 3.83 (s, 2H), 4.67 (s, 2H), 6.96 7.21 (m, 2H), 7.31 (d, 1H, J = 7.6 Hz), 7.46 (br s, 1H), 8.15 (br s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 23.6, 28.5, 28.6, 40.8, 41.6, 80.1, 107.5, 110.9, 117.6, 119.6, 121.6, 125.7, 128.4, 131.8, 132.3, 136.0, 155.4; HRMS calcd. for C 16 H 21 2 O 2 (M + +1) 273.1603, found 273.1611. 3h. Benzyl 3,4-dihydro-1H-pyrido[4,3-b]indole-2(5H)-carboxylate: Cbz H Colorless oil; Yield 94%; IR (neat): 3315, 1684, 1615, 1425, 1219, 731 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 2.85 (s, 2H), 3.90 (d, 2H, J = 5.2 Hz), 4.75 (s, 2H), 5.22 (s, 2H), 7.09 7.20 (m, 2H), 7.29 7.48 (m, 7H), 8.0 (s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 23.5, 23.8, 41.5, 67.4, 107.1, 110.9, 117.7, 119.7, 121.8, 128.1, 128.2, 128.5, 128.6, 132.0, 136.0, 136.8, 156.1; HRMS calcd. for C 19 H 19 2 O 2 (M + +H) 307.1447, found 307.1448. 3i. 5,10-Dihydroindeno[1,2-b]indole: H Colorless solid; Yield 97%; M.p. 232 234 o C; IR (neat): 3404, 1446, 737 cm -1 ; 1 H MR (400 MHz, MeOD): δ 2.92 2.98 (m, 2H), 6.66 6.67 (m, 2H) 6.79 6.86 (m, 1H), 6.95 (dd, 1H, J = 12.8, 5.6 Hz), 7.06 (d, 1H, J = 8.0 Hz), 7.13 7.23 (m, 3H); 13 C MR (100 MHz, MeOD): δ 30.8, 113.1, 118.5, 119.4, 120.5, 121.5, 122.1, 125.6, 125.9, 126.3, 127.5, 136.8, 149.1, 145.0, 142.5; HRMS calcd. for C 15 H 12 1 (M + +1) 206.0970, found 206.0967. 3j. 3-Methyl-2-phenyl-1H-indole: CH 3 H Ph S4

Colorless solid; Yield 97%; M.p. 93 94 o C; IR (neat): 3337, 3054, 1607, 1583, 1536, 1449, 1265 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 2.35 (s, 3H), 7.03 7.13 (m, 2H), 7.20 7.26 (m, 2H), 7.33 7.39 (m, 2H), 7.42 7.47 (m, 2H), 7.50 (d, 1H, J = 7.6 Hz), 7.83 (br s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 9.8, 108.8, 110.8, 119.1, 119.6, 122.4, 127.4, 127.8, 128.9, 130.2, 133.5, 134.1, 136.0; HRMS calcd. for C 15 H 14 (M + +H) 208.1126, found 208.1126. 3k. 3-Isopropyl-2-methyl-1H-indole: H 3 C CH 3 H Yellow oil; Yield 95%; IR (neat): 3392, 2963, 1608, 1462, 1022 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.40 (d, 6H, J = 7.2 Hz), 2.35 (s, 3H), 3.17 (sep, 1H, J = 7.2 Hz), 7.01 7.11(m, 2H), 7.22 (d, 1H, J = 7.2 Hz), 7.58 (s, 1H), 7.65 (d, 1H, J = 7.2 Hz); 13 C MR (100 MHz, CDCl 3 ): δ 12.2, 23.1, 26.0, 110.4, 117.9, 118.8, 119.5, 120.6, 127.5, 129.3, 135.5; HRMS calcd. for C 12 H 16 (M + +1) 174.1283, found 174.1289. 3l. 3-(1H-Indol-3-yl)propan-1-ol: CH 3 OH H Yellow oil; Yield 80%; IR (neat): 3200 3500, 1457, 1024, 741 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.96 2.03 (quin, 2H, J = 6.4 Hz ), 2.86 (t, 2H, J = 7.6 Hz), 3.73 (t, 2H, J = 6.4 Hz), 6.99 (s, 1H), 7.10 7.16 (m, 1H), 7.17 7.23 (m, 1H), 7.35 (d, 1H, J = 8.0 Hz), 7.62 (d, 1H, J = 8.0 Hz), 8.0 (s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 21.5, 33.0, 62.8, 111.2, 116.0, 119.0, 119.3, 121.4, 122.1, 127.6, 136.5; HRMS calcd. for C 11 H 14 O (M + +1) 176.1075, found 176.1078. 3m. 2-(1H-Indol-3-yl)ethanol: H Colorless oil; Yield 90%; IR (neat): 3400 3100, 1660, 1493, 1282, 1034 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 3.05 (t, 2H, J = 6.0 Hz), 3.92 (t, 2H, J = 6.4 Hz), 7.09 7.18 (m, 2H), 7.19 7.25 (m, 1H), 7.38 (d, 1H, J = 8.4 Hz), 7.63 (d, 1H, J = 7.6 Hz), 8.10 (br s, 1H); 13 C MR (125 MHz, CDCl 3 ): δ 28.8, 62.6, 111.2, 112.3, 118.9, 119.5, 122.2, 122.5, 127.4, 136.5; HRMS calcd. for C 10 H 12 O (M + +H) 162.0919, found 162.0924. OH S5

3n. (S)-Dimethyl 2-(2,3,4,9-tetrahydro-1H-carbazol-2-yl)malonate: H CO 2 Me CO 2 Me Colorless solid; Yield 97%; [α] 20 D = 28.20 (c 1.0, CHCl 3 ); M.p. 117 119 o C; IR (neat): 3200 3400, 2932, 1564, 1039 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.50 1.65 (m, 1H), 1.89 2.0 (m, 1H), 2.50 2.83 (m, 5H), 3.41 (d, 1H, J = 8.8 Hz, CH(COOCH 3 ) 2 ), 3.68 (s, 3H, COOCH 3 ), 3.70 (s, 3H, COOCH 3 ), 6.94 7.07 (m, 2H), 7.17 (d, 1H, J = 8.0 z), 7.37 (d, 1H, J = 7.6 Hz), 7.65 (br s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 20.1, 27.1, 27.6, 34.8, 52.6 (COOCH 3 ), 52.7 (COOCH 3 ), 56.5 (CH(COOCH 3 ) 2 ), 109.5, 110.6, 117.9, 119.3, 121.3, 127.4, 132.4, 136.0, 169.1 (C=O), 169.2 (C=O); HRMS calcd. for C 17 H 23 2 O 3 (M + +a): 324.1212, found 324.1214. 3o. 6,7,8,9,10,11-Hexahydro-5H-cycloocta[b]indole: H Colorless solid; Yield 96%; M.p. 162 163 o C; IR (neat): 3410, 3048, 1451, 1319, 743 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 2.95 3.01 (m, 2H), 3.03 3.10 (m, 2H), 7.09 7.20 (m, 3H), 7.22 7.29 (m, 2H), 7.32 (d, 1H, J = 6.8 Hz), 7.38 (d, 1H, J = 8.0 Hz), 7.55 (d, 1H, J = 7.8 Hz) 8.19 (br s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 19.8, 29.7, 111.2, 112.8, 118.9, 119.9, 120.0, 122.5, 126.8, 126.9, 127.6, 128.6, 129.0, 133.2, 136.7, 137.1; HRMS calcd. for C 16 H 14 1 (M + +1) 220.1126, found 220.1125. 5a. 4a-Methyl-2,3,4,4a-tetrahydro-1H-carbazole: H 3 C Pale yellow oil; Yield 99%; IR (neat): 1582, 1444, 1190 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.16 (td, 1H, J = 13.2, 4.0 Hz), 1.30 (s, 3H), 1.33 1.48 (m, 1H), 1.64 1.86 (m, 2H), 2.12 2.32 (m, 2H), 2.58 (td, 1H, J = 13.2, 5.6 Hz), 2.86 (d, 1H, J = 13.2 Hz), 7.19 (t, 1H, J = 7.2 Hz), 7.25 7.38 (m, 2H), 7.59 (d, 1H, J = 7.6 Hz); 13 C MR (100 MHz, CDCl 3 ): δ 19.9, 21.5, 29.1, 29.8, 38.7, 53.9, 120.3, 121.4, 124.9, 127.6, 146.9, 154.3, 190.3; HRMS calcd. for C 13 H 16 1 (M + +1) 186.1283, found 186.1276. 5b. Ethyl 3-(2,3,4,4a-tetrahydro-1H-carbazol-4a-yl)propanoate: S6

OEt O Colorless oil; Yield 94%; IR (neat): 2930, 1725, 1583, 1451, 1377, 1174, 738 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.15 (t, 3H, J = 7.2 Hz, COOCH 2 CH 3 ), 1.18 1.27 (m, 1H), 1.35 1.49 (m, 1H), 1.52 1.66 (m, 2H), 1.66 1.74 (m, 1H), 1.79 1.93 (m, 1H), 2.11 2.25 (m, 2H), 2.31 2.47 (m, 2H), 2.55 (dt, 1H, J = 13.2, 5.6 Hz), 2.85 2.92 (m, 1H), 3.95 4.04 (m, 2H, COOCH 2 CH 3 ), 7.17 7.22 (m, 1H), 7.25 7.29 (m, 1H), 7.30 7.35 (m, 1H), 7.59 (d, 1H, J = 7.6 Hz); 13 C MR (100 MHz, CDCl 3 ): δ 14.1 (CH 3 ), 21.2, 28.6, 28.7, 29.1, 30.1, 38.3, 57.5, 60.5 (OCH 2 ), 120.4, 121.7, 125.1, 127.9, 143.9, 155.1, 173.1 (C=O), 188.6 (C=); HRMS calcd. for C 17 H 22 O 2 (M + +1): 272.1651, found 272.1651. 5c. 4a-(2-Azidoethyl)-2,3,4,4a-tetrahydro-1H-carbazole: 3 Colorless liquid; Yield 92%; IR (neat): 2920, 2857, 2157, 2091, 1584, 1446, 1258, 758 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.18 (td, 1H, J = 13.6, 4.0 Hz), 1.40 1.51 (m, 1H), 1.66 1.75 (m, 1H), 1.76 1.86 (m, 1H), 2.07 2.15 (m, 1H), 2.18 2.26 (m, 1H), 2.32 2.44 (m, 2H), 2.55 2.65 (m, 2H, CH 2 3 ), 2.67 2.76 (m, 1H, =CCH 2 ), 2.89 2.97 (m, 1H, =CCH 2 ), 7.22 (d, 1H, J = 7.2 Hz), 7.27 (d, 1H, J = 7.6 Hz), 7.35 (t, 1H, J = 7.2 Hz), 7.61 (d, 1H, J = 7.6 Hz); 13 C MR (100 MHz, CDCl 3 ): δ 21.3, 29.2, 30.3, 33.2, 39.0, 47.1 (CH 2 3 ), 56.7, 120.6, 121.5, 125.2, 128.2, 143.5, 155.0, 188.4 (C=); HRMS calcd. for C 14 H 17 4 (M + +H) 241.1453, found 241.1453. 5d. 4a-Allyl-2,3,4,4a-tetrahydro-1H-carbazole: Pale yellow oil; Yield 90%; IR (neat): 2935, 1584, 1448, 920, 762 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.15 (td, 1H, J = 13.6, 4.0 Hz), 1.36 1.51 (m, 1H), 1.64 1.74 (m, 1H), 1.80 1.90 (m, 1H), 2.15 2.25 (m, 1H), 2.32 2.41 (m, 1H) 2.51 2.67 (m, 3H), 2.84 2.93 (m, 1H), 4.85 (d, 1H, J = 10.0 Hz), 4.94 (d, 1H, J = 16.8 Hz), 5.10 5.23 (m, 1H), 7.15 7.23 (m, 1H), 7.28 7.38 (m, 2H), 7.58 (d, 1H, J = 7.6 Hz); 13 C MR (100 MHz, CDCl 3 ): δ 21.2, 29.0, 30.3,. 37.0, 37.8, 57.8, 118.1, 120.2, 122.0, 124.8, 127.7, 132.3, 144.7, 155.0, 189.0; HRMS calcd. for C 15 H 18 1 (M + +1) 212.1439, found 212.1443. 5e. 3-(2,3,4,4a-Tetrahydro-1H-carbazol-4a-yl)propanenitrile: S7

C Pale yellow oil; Yield 90%; IR (neat): 1582, 1444, 1190 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.25 (td, 1H, J = 13.6, 4.8 Hz), 1.39 1.52 (m, 1H), 1.59 (t, 2H, J = 8.4 Hz), 1.74 1.86 (m, 2H), 2.15 2.30 (m, 2H), 2.32 2.41 (m, 1H), 2.47 2.58 (m, 2H), 2.91 3.0 (m, 1H), 7.23 7.30 (m, 2H), 7.35 7.41 (m, 1H), 7.62 (d, 1H, J = 7.6 Hz); 13 C MR (100 MHz, CDCl 3 ): δ 12.1, 21.3, 29.1, 29.9, 30.3, 38.2, 57.4, 119.1, 120.9, 121.6, 125.7, 128.7, 142.4, 155.1, 187.3; HRMS calcd. for C 15 H 17 2 (M + +1) 225.1392, found 225.1393. 10. 6-Chloro-2,3,4,9-tetrahydro-1H-carbazole: Cl Colorless solid; Yield 97%; M.p. 162 163 o C; IR (neat): 3404, 2356, 1686, 1440, 799 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.80 1.96 (m, 4H), 2.66 (t, 2H, J = 6.0 Hz), 2.72 (t, 2H, J = 5.6 Hz), 7.05 (dd, 1H, J = 8.4, 1.6 Hz), 7.17 (d, 1H, J = 8.4 Hz), 7.41 (s, 1H), 7.70 (s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 20.9, 23.1, 23.2, 23.4, 110.2, 111.3, 117.5, 121.2, 124.9, 129.1, 134.1, 135.9; HRMS calcd. for C 12 H 13 Cl (M + +1) 206.0737, found 206.0736. 11. 6,8-Dichloro-2,3,4,9-tetrahydro-1H-carbazole: Cl Cl Pale yellow solid; Yield 90%; M.p. 64 65 o C; IR (neat): 3437, 2928, 1571, 1465, 858 cm - 1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.79 1.93 (m, 4H), 2.57 2.63 (m, 2H), 2.70 (t, 2H, J = 5.6 Hz), 7.07 (s, 1H), 7.28 (s, 1H), 7.86 (br s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 20.9, 23.0, 23.1, 23.3, 111.3, 116.1, 116.3, 120.3, 124.7, 129.8, 131.4, 136.6; HRMS calcd. for C 12 H 11 Cl 2 (M + ) 240.0347, found 240.0340. 12. 6-Methyl-2,3,4,9-tetrahydro-1H-carbazole: Me Colorless solid; Yield 96%; M.p. 142 144 o C; IR (neat): 3391, 2922, 1457, 795 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.81 1.94 (m, 4H), 2.43 (s, 3H), 2.64 2.73 (m, 4H), 6.92 (dd, 1H, J = 8.4, 1.2 Hz), 7.15 (d, 1H, J = 8.0 Hz), 7.24 (s, 1H), 7.54 (br s, 1H); 13 C MR H H H S8

(100 MHz, CDCl 3 ): δ 21.1, 21.6, 23.3, 23.4, 23.5, 109.8, 110.1, 117.7, 122.5, 128.2, 128.4, 134.0, 134.4; HRMS calcd. for C 13 H 16 (M + +1) 186.1283, found 186.1289. 13. 6-Methoxy-2,3,4,9-tetrahydro-1H-carbazole: MeO Colorless solid; Yield 95%; M.p. 106 108 o C; IR (neat): 3390, 2916, 1590, 1484, 1219, 1028 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.84 1.97 (m, 4H), 2.67 2.75 (m, 4H), 3.88 (s, 3H), 6.79 (dd, 1H, J = 8.8, 2.0 Hz), 6.92 (d, 1H, J = 2.4 Hz), 7.16 (d, 1H, J = 8.4 Hz), 7.59 (s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 21.1, 23.3, 23.4, 23.5, 56.1, 100.4, 110.1, 110.6, 111.1, 128.3, 130.8, 135.2, 154.0; HRMS calcd. for C 13 H 16 O (M + +H) 202.1232, found 202.1228. 14. Tert-butyl 8-methoxy-3,4-dihydro-1H-pyrido[4,3-b]indole-2(5H)-carboxylate: MeO H Colorless solid; Yield 88%; M.p. 174 176 o C (dec); IR (neat): 3304, 1674, 1426, 735 cm - 1 ; 1 H MR (500 MHz, CDCl 3 ): δ 1.53 (s, 9H), 2.79 (s, 2H), 3.81 (s, 2H), 3.86 (s, 3H), 4.62 (s, 2H), 6.81 (d, 1H, J = 8.0 Hz), 6.91 (s, 1H), 7.19 (d, 1H, J = 7.0 Hz), 8.09 (br s, 1H); 13 C MR (125 MHz, CDCl 3 ): δ 23.7, 28.6, 40.8, 41.6, 56.0, 80.0, 100.1, 107.3, 111.3, 111.5, 126.1, 131.1, 132.7, 133.3, 154.2, 155.4; HRMS calcd. for C 17 H 23 2 O 3 (M + +1) 303.1709, found 303.1724. 15. 3-(5,7-Dichloro-1H-indol-3-yl)propan-1-ol: H O O Cl OH Cl H Pale yellow oil; Yield 90%; IR (neat): 3200 3400, 2932, 1564, 1039 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.95 (quin, 2H, J = 6.4 Hz, CH 2 -CH 2 -CH 2 ), 2.80 (t, 2H, J = 7.6 Hz), 3.71 (t, 2H, J = 6.4 Hz, CH 2 -OH), 7.07 (d, 1H, J = 2.0 Hz), 7.18 (d, 1H, J = 1.6 Hz), 7.48 (d, 1H, J = 1.6 Hz), 8.27 (br s, 1H, H); 13 C MR (100 MHz, CDCl 3 ): δ 21.4, 32.9, 62.4 (CH 2 -OH), 117.1, 117.2, 117.4, 121.6, 123.4, 125.0, 129.5, 132.3; HRMS calcd. for C 11 H 12 OCl 2 (M + +1) 244.0296, found 244.0304. 16. 2-(5-Methoxy-1H-indol-3-yl)ethanol: S9

MeO OH Colorless oil; Yield 92%; IR (neat): 3100 3400, 1493, 1282, 1034, 826 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 3.0 (t, 2H, J = 6.4 Hz), 3.87 (s, 3H), 3.90 (t, 2H, J = 6.4 Hz), 6.87 (dd, 1H, J = 8.8, 2.4 Hz), 7.05 (d, 2H, J = 2.2 Hz), 7.25 (d, 1H, J = 8.8 Hz), 8.04 (br s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 28.8, 56.1, 62.7, 100.7, 112.0, 112.1, 112.5, 123.4, 127.9, 131.7, 154.1; HRMS calcd. for C 11 H 14 O 2 (M + +H) 192.1025, found 192.1021. 16A. 3-(2-Iodoethyl)-5-methoxy-1H-indole: H MeO I Colorless solid; Yield 97%; 1 H MR (400 MHz, CDCl 3 ): δ 3.28 3.35 (m, 2H), 3.38 3.45 (m, 2H), 3.86 (s, 3H), 6.85 (dd, 1H, J = 8.8, 2.4 Hz), 6.98 (d, 1H, J = 2.4 Hz), 7.04 (d, 1H, J = 2.0 Hz), 7.24 (d, 1H, J = 2.4 Hz), 7.99 (br s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 6.3, 30.5, 56.1, 100.4, 112.2, 112.5, 115.4, 122.8, 127.3, 131.4, 154.2. 16B. 3-(2-Azidoethyl)-5-methoxy-1H-indole: H MeO 3 Colorless oil; Yield 96%; 1 H MR (400 MHz, CDCl 3 ): δ 3.02 (t, 2H, J = 7.2 Hz), 3.55 (t, 2H, J = 7.2 Hz), 3.87 (s, 3H), 6.87 (dd, 1H, J = 8.8, 2.4 Hz), 7.01 7.04 (m, 2H), 7.23 (d, 1H, J = 8.8 Hz), 7.96 (br s, 1H); 13 C MR (100 MHz, CDCl 3 ): δ 25.2, 51.7, 56.1, 100.5, 112.1, 112.5, 123.2, 127.6, 131.5, 154.2. IV. -(2-(5-Methoxy-1H-indol-3-yl)ethyl)acetamide: MeO H Colorless solid; Yield 95%; M.p. 118 120 o C; IR (neat): 3402, 1650, 1627, 1397, 1038 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 1.81 (s, 3H), 2.83 (t, 2H, J = 6.8 Hz), 3.47 (q, 2H, J = 6.4 Hz), 3.75 (s, 3H), 5.62 (br s, 1H), 6.76 (dd, 2H, J = 8.8, 2.4 Hz), 6.88 (d, 1H, J = 2.0 Hz), 6.93 (d, 1H, J = 2.4 Hz); 13 C MR (100 MHz, CDCl 3 ): δ 23.4, 25.4, 39.9, 56.1, 100.6, 112.2, 112.4, 112.6, 123.0, 127.8, 131.7, 154.1, 170.4; HRMS calcd. for C 13 H 17 2 O 2 (M + +H) 233.1290, found 233.1289. H H CH 3 17. 2-Methyl-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole: O S10

Me Me Colorless solid; Yield 91%; M.p. 97 99 o C; IR (neat): 3334, 2923, 1634, 1463, 795 cm -1 ; 1 H MR (400 MHz, CDCl 3 ): δ 2.43 (s, 3H), 2.58 (s, 3H), 2.85 (s, 4H), 3.69 (s, 2H), 6.94 (d, 1H, J = 8.4 Hz), 7.15 (s, 1H), 7.17 (d, 2H, J = 3.6 Hz); 13 C MR (100 MHz, CDCl 3 ): δ 21.6, 23.7, 45.7, 51.8, 52.5, 107.9, 110.4, 117.5, 122.8, 126.4, 128.6, 131.8, 134.5; HRMS calcd. for C 13 H 17 2 (M + +1) 201.1392, found 201.1384. H S11

H Expanded 1 H MR spectra of compound 3a S12

S13 Expanded 1 H MR spectrum of indole derivative 3a

H 13 C MR spectrum of indole derivative 3a S14

H 1 H MR spectrum of indole derivative 3b S15

S16 Expanded 1 H MR spectrum of indole derivative 3b

H 13 C MR spectrum of indole derivative 3b S17

H 1 H MR spectrum of indole derivative 3c S18

S19 Expanded 1 H MR spectrum of indole derivative 3c

H 13 C MR spectrum of indole derivative 3c S20

H 1 H MR spectrum of indole derivative 3d S21

S22 Expanded 1 H MR spectrum of indole derivative 3d

H 13 C MR spectrum of indole derivative 3d S23

CH 3 H 3 C H 1 H MR spectrum of indole derivative 3e S24

S25 Expanded 1 H MR spectrum of indole derivative 3e

CH 3 H 3 C H 13 C MR spectrum of indole derivative 3e S26

Ph H 1 H MR spectrum of indole derivative 3f S27

S28 Expanded 1 H MR spectrum of indole derivative 3f

Ph H 13 C MR spectrum of indole derivative 3f S29

Current Data Parameters AME sb40712 EXPO 64 PROCO 1 F2 - Acquisition Parameters Date_ 20120707 Time 10.25 ISTRUM spect PROBHD 5 mm PABBO BB- PULPROG zg30 TD 32768 SOLVET CDCl3 S 32 DS 2 SWH 8417.509 Hz FIDRES 0.256882 Hz AQ 1.9464692 sec RG 67.99 DW 59.400 usec DE 6.50 usec TE 295.0 K D1 0.50000000 sec TD0 1 ======== CHAEL f1 ======== UC1 1H P1 17.00 usec PLW1 7.75000000 W SFO1 400.1338012 MHz F2 - Processing parameters SI 65536 SF 400.1300094 MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC 1.00 1. 5 3 3 2. 7 9 9 2. 8 1 3 2. 8 2 7 3. 8 2 9 4. 6 6 7 7. 0 9 5 7. 1 1 2 7. 1 3 1 7. 1 4 7 7. 1 6 6 7. 1 8 3 7. 2 6 0 7. 3 0 1 7. 3 2 0 7. 4 5 8 8. 1 5 3 lab sb sb-sg-1727 iitm_proto-1to20 CDCl3 /opt/topspin nmr 2 Boc H 9 8 7 6 5 4 3 2 1 0 ppm 9. 2 3 9 2. 0 0 2 2. 0 0 0 2. 0 1 5 2. 0 1 9 0. 9 9 3 1. 0 3 9 0. 9 5 5 1 H MR spectrum of indole derivative 3g S30

8.153 7.458 7.301 7.320 7.260 7.095 7.112 7.131 7.147 7.166 7.183 lab sb sb-sg-1727 iitm_proto-1to20 CDCl3 /opt/topspin nmr 2 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 ppm 4.667 3.829 2.827 2.813 2.799 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 ppm 2.84 2.82 2.80 2.78 ppm Expanded 1 H MR spectrum of indole derivative 3g S31

Current Data Parameters AME sb40712 EXPO 70 PROCO 1 F2 - Acquisition Parameters Date_ 20120707 Time 15.54 ISTRUM spect PROBHD 5 mm PABBO BB- PULPROG zgpg30 TD 16540 SOLVET CDCl3 S 5606 DS 4 SWH 24038.461 Hz FIDRES 1.453353 Hz AQ 0.3440820 sec RG 200.34 DW 20.800 usec DE 6.50 usec TE 297.0 K D1 1.00000000 sec D11 0.03000000 sec TD0 1 ======== CHAEL f1 ======== UC1 13C P1 9.25 usec PLW1 47.00000000 W SFO1 100.6228289 MHz ======== CHAEL f2 ======== CPDPRG2 waltz16 UC2 1H PCPD2 90.00 usec PLW2 7.75000000 W PLW12 0.27651000 W PLW13 0.22397999 W SFO2 400.1316005 MHz F2 - Processing parameters SI 32768 SF 100.6127615 MHz WDW EM SSB 0 LB 3.00 Hz GB 0 PC 1.40 2 3. 6 2 7 2 8. 4 9 3 2 8. 6 2 1 4 0. 7 8 9 4 1. 5 5 3 7 6. 8 4 2 7 7. 1 6 0 7 7. 4 7 7 8 0. 0 5 0 1 0 7. 4 7 0 1 1 0. 8 8 4 1 1 7. 6 4 3 1 1 9. 6 0 6 1 2 1. 6 4 0 1 2 5. 6 7 5 1 2 8. 4 4 4 1 3 1. 8 3 0 1 3 2. 3 2 9 1 3 6. 0 2 7 1 5 5. 4 3 3 Boc lab sb sb-sg-1727 iitm_carbonshort CDCl3 /opt/topspin nmr 1 H 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm 13 C MR spectrum of indole derivative 3g S32

Current Data Parameters AME sb40712 EXPO 72 PROCO 1 F2 - Acquisition Parameters Date_ 20120707 Time 18.00 ISTRUM spect PROBHD 5 mm PABBO BB- PULPROG deptsp135 TD 32768 SOLVET CDCl3 S 1335 DS 4 SWH 20161.291 Hz FIDRES 0.615274 Hz AQ 0.8126964 sec RG 200.34 DW 24.800 usec DE 6.50 usec TE 296.2 K CST2 145.0000000 D1 1.00000000 sec D2 0.00344828 sec D12 0.00002000 sec TD0 1 ======== CHAEL f1 ======== UC1 13C P1 9.25 usec P13 2000.00 usec PLW0 0 W PLW1 47.00000000 W SFO1 100.6208166 MHz SPAM5 Crp60comp.4 SPOAL5 0.500 SPOFFS5 0 Hz SPW5 6.14429998 W ======== CHAEL f2 ======== CPDPRG2 waltz16 UC2 1H P3 17.00 usec P4 34.00 usec PCPD2 90.00 usec PLW2 7.75000000 W PLW12 0.27651000 W SFO2 400.1312797 MHz F2 - Processing parameters SI 32768 SF 100.6127690 MHz WDW EM SSB 0 LB 3.00 Hz GB 0 PC 1.40 23.542 28.550 40.713 41.512 110.821 117.567 119.531 121.565 Boc lab sb sb-sg-1727 iitm_c13dept135 CDCl3 /opt/topspin nmr 1 H 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm 13 C DEPT MR spectrum of indole derivative 3g S33

lab sb sb-sg-1727 COSYGPSW CDCl3 /opt/topspin nmr 1 ppm 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 Current Data Parameters AME sb40712 EXPO 74 PROCO 1 F2 - Acquisition Parameters Date_ 20120707 Time 18.41 ISTRUM spect PROBHD 5 mm PABBO BB- PULPROG cosygpppqf TD 2048 SOLVET CDCl3 S 1 DS 8 SWH 3703.704 Hz FIDRES 1.808449 Hz AQ 0.2765300 sec RG 28.27 DW 135.000 usec DE 6.50 usec TE 295.7 K D0 0.00000300 sec D1 1.91521299 sec D11 0.03000000 sec D12 0.00002000 sec D13 0.00000400 sec D16 0.00020000 sec I0 0.00027000 sec ======== CHAEL f1 ======== UC1 1H P0 17.00 usec P1 17.00 usec P17 2500.00 usec PLW1 7.75000000 W PLW10 3.31320000 W SFO1 400.1317751 MHz ====== GRADIET CHAEL ===== GPAM1 SMSQ10.100 GPZ1 10.00 % P16 1000.00 usec F1 - Acquisition parameters TD 128 SFO1 400.1318 MHz FIDRES 28.935184 Hz SW 9.256 ppm FnMODE QF F2 - Processing parameters SI 1024 SF 400.1300511 MHz WDW QSIE SSB 0 LB 0 Hz GB 0 PC 1.40 F1 - Processing parameters SI 1024 MC2 QF SF 400.1300511 MHz WDW SSB 0 LB 0 Hz GB 0 Boc H 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 8 7 6 5 4 3 2 1 ppm 11 H 1 H COSY MR spectrum of indole derivative 3g S34

O Ph O H 1 H MR spectrum of indole derivative 3h S35

S36 Expanded 1 H MR spectrum of indole derivative 3h

O O Ph H 13 C MR spectrum of indole derivative 3h S37

Ph O O H 13 C DEPT MR spectrum of indole derivative 3h S38

1 H 1 H COSY MR spectrum of indole derivative 3h O O Ph H S39

H 1 H MR spectrum of indole derivative 3i S40

S41 Expanded 1 H MR spectrum of indole derivative 3i

13 C MR spectrum of indole derivative 3i H S42

Ph H 3 C H 1 H MR spectrum of indole derivative 3j S43

S44 Expanded 1 H MR spectrum of indole derivative 3j

Ph H 3 C H 13 C MR spectrum of indole derivative 3j S45

H3 C H 3 C CH 3 H 1 H MR spectrum of indole derivative 3k S46

S47 Expanded 1 H MR spectrum of indole derivative 3k

H3 C H 3 C CH 3 H 13 C MR spectrum of indole derivative 3k S48

HO H 1 H MR spectrum of indole derivative 3l S49

S50 Expanded 1 H MR spectrum of indole derivative 3l

HO H 13 C MR spectrum of indole derivative 3l S51

OH H 1 H MR spectrum of indole derivative 3m S52

S53 1 H MR expansion spectrum of indole derivative 3m

OH H 13 C MR spectrum of indole derivative 3m S54

MeO 2 C CO 2 Me H 1 H MR spectrum of indole derivative 3n S55

S56 Expanded 1 H MR spectrum of indole derivative 3n

MeO 2 C CO 2 Me H 13 C MR spectrum of indole derivative 3n S57

MeO 2 C CO 2 Me H 13 C DEPT MR spectrum of indole derivative 3n S58

MeO 2 C CO 2 Me 1 H 1 H 1 H COSY MR MR spectrum spectra of indole compound derivative 3n 3n H S59

H 1 H MR spectrum of indole derivative 3o S60

S61 Expanded 1 H MR spectrum of indole derivative 3o

H 13 C MR spectrum of indole derivative 3o S62

H 3 C 1 H MR spectrum of indolenine derivative 5a S63

S64 Expanded 1 H MR spectrum of indolenine derivative 5a

H 3 C 13 C MR spectrum of indolenine derivative 5a S65

EtOOC 1 H MR spectrum of indolenine derivative 5b S66

S67 Expanded 1 H MR spectrum of indolenine derivative 5b

S68 Expanded 1 H MR spectrum of indolenine derivative 5b

EtOOC 13 C MR spectrum of indolenine derivative 5b S69

EtOOC 13 C DEPT MR spectrum of indolenine derivative 5b S70

EtOOC 1 H 1 H COSY MR spectrum of indolenine derivative 5b S71

3 1 H MR spectrum of indolenine derivative 5c S72

S73 Expanded 1 H MR spectrum of indolenine derivative 5c

S74 Expanded 1 H MR spectrum of indolenine derivative 5c

3 13 C MR spectrum of indolenine derivative 5c S75

13 C DEPT MR spectrum of indolenine derivative 5c 3 S76

3 1 H 1 H COSY MR spectrum of indolenine derivative 5c S77

1 H MR spectrum of indolenine derivative 5d S78

S79 Expanded 1 H MR spectrum of indolenine derivative 5d

S80 Expanded 1 H MR spectrum of indolenine derivative 5d

13 C MR spectrum of indolenine derivative 5d S81

13 C DEPT MR spectrum of indolenine derivative 5d S82

1 H 1 H COSY MR spectrum of indolenine derivative 5d S83

C 1 H MR spectrum of indolenine derivative 5e S84

S85 Expanded 1 H MR spectrum of indolenine derivative 5e

S86 Expanded 1 H MR spectrum of indolenine derivative 5e

C 13 C MR spectrum of indolenine derivative 5e S87

13 C DEPT MR spectrum of indolenine derivative 5e C S88

C 1 H 1 H COSY MR spectrum of indolenine derivative 5e S89

H Cl 1 H MR spectrum of indole derivative 10 S90

S91 Expanded 1 H MR spectrum of indole derivative 10

Cl H 13 C MR spectrum of indole derivative 10 S92

1 H MR spectrum of indole derivative 11 H Cl Cl S93

S94 Expanded 1 H MR spectrum of indole derivative 11

13 C MR spectrum of indole derivative 11 H Cl Cl S95

H 1 H MR spectrum of indole derivative 12 Me S96

S97 Expanded 1 H MR spectrum of indole derivative 12

Me H 13 C MR spectrum of indole derivative 12 S98

Current Data Parameters AME sb40612 EXPO 171 PROCO 1 F2 - Acquisition Parameters Date_ 20120630 Time 11.44 ISTRUM spect PROBHD 5 mm PABBO BB- PULPROG zg30 TD 65536 SOLVET CDCl3 S 16 DS 2 SWH 8012.820 Hz FIDRES 0.122266 Hz AQ 4.0894966 sec RG 95.73 DW 62.400 usec DE 6.50 usec TE 294.6 K D1 0.50000000 sec TD0 1 ======== CHAEL f1 ======== UC1 1H P1 17.00 usec PLW1 7.75000000 W SFO1 400.1320007 MHz F2 - Processing parameters SI 65536 SF 400.1300093 MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC 1.00 1.899 1.912 1.926 2.697 2.711 2.724 3.880 6.779 6.784 6.801 6.806 6.952 7.147 7.169 7.260 7.555 MeO sb-sg-1007 iitm_proto-5to15 CDCl3 /opt/topspin nmr 9 H 9 8 7 6 5 4 3 2 1 0 ppm 4.000 3.991 2.947 0.937 0.956 0.950 0.925 1 H MR spectrum of indole derivative 13 S99

7.555 7.260 7.147 7.169 6.952 6.779 6.784 6.801 6.806 lab sb sb-sg-1007 iitm_proto-5to15 CDCl3 /opt/topspin nmr 9 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 ppm 2.697 2.711 2.724 3.880 1.899 1.912 1.926 3.89 3.88 3.87 ppm 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 ppm Expanded 1 H MR spectrum of indole derivative 13 S100

Current Data Parameters AME sb40612 EXPO 172 PROCO 1 F2 - Acquisition Parameters Date_ 20120630 Time 12.08 ISTRUM spect PROBHD 5 mm PABBO BB- PULPROG zgpg30 TD 16540 SOLVET CDCl3 S 1000 DS 4 SWH 24038.461 Hz FIDRES 1.453353 Hz AQ 0.3440820 sec RG 200.34 DW 20.800 usec DE 6.50 usec TE 295.8 K D1 1.00000000 sec D11 0.03000000 sec TD0 1 ======== CHAEL f1 ======== UC1 13C P1 9.25 usec PLW1 47.00000000 W SFO1 100.6228289 MHz ======== CHAEL f2 ======== CPDPRG2 waltz16 UC2 1H PCPD2 90.00 usec PLW2 7.75000000 W PLW12 0.27651000 W PLW13 0.22397999 W SFO2 400.1316005 MHz F2 - Processing parameters SI 32768 SF 100.6127595 MHz WDW EM SSB 0 LB 1.00 Hz GB 0 PC 1.40 21.095 23.332 23.442 56.112 76.843 77.160 77.478 100.409 110.126 110.630 111.084 128.319 130.847 135.244 153.968 MeO H sb-sg-1007 iitm_carbonshort CDCl3 /opt/topspin nmr 9 200 180 160 140 120 100 80 60 40 20 0 ppm 13 C MR spectrum of indole derivative 13 S101

Current Data Parameters AME sb50712 EXPO 42 PROCO 1 F2 - Acquisition Parameters Date_ 20120707 Time 12.14 ISTRUM spect PROBHD 5 mm PABBO BB/ PULPROG zg30 TD 32768 SOLVET CDCl3 S 32 DS 2 SWH 10000.000 Hz FIDRES 0.305176 Hz AQ 1.6384500 sec RG 31.24 DW 50.000 usec DE 6.50 usec TE 298.1 K D1 0.50000000 sec TD0 1 ======== CHAEL f1 ======== UC1 1H P1 11.75 usec PLW1 15.30000019 W SFO1 500.1530886 MHz F2 - Processing parameters SI 65536 SF 500.1500129 MHz WDW EM SSB 0 LB 0.30 Hz GB 0 PC 1.00 1.526 2.788 3.811 3.864 4.622 6.803 6.819 6.906 7.183 7.197 7.260 8.092 Boc MeO 9 8 7 6 5 4 3 2 1 0 ppm Lab SB sb/sg/1728 iitm_proto CDCl3 /opt/topspin iitm 15 H 1.019 0.956 1.809 2.000 5.134 2.018 9.384 1 H MR spectrum of indole derivative 14 S102

8.092 7.260 7.183 7.197 6.906 6.803 6.819 Lab SB sb/sg/1728 iitm_proto CDCl3 /opt/topspin iitm 15 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 ppm 1.526 4.622 3.811 3.864 2.788 1.54 1.52 1.50 1.48 1.46 ppm 4.6 4.4 4.2 4.0 3.8 3.6 3.4 3.2 3.0 2.8 ppm Expanded 1 H MR spectrum of indole derivative 14 S103

Current Data Parameters AME sb50712 EXPO 51 PROCO 1 F2 - Acquisition Parameters Date_ 20120708 Time 19.06 ISTRUM spect PROBHD 5 mm PABBO BB/ PULPROG zgpg30 TD 20480 SOLVET CDCl3 S 12288 DS 4 SWH 29761.904 Hz FIDRES 1.453218 Hz AQ 0.3441140 sec RG 202.34 DW 16.800 usec DE 6.50 usec TE 297.8 K D1 1.00000000 sec D11 0.03000000 sec TD0 1 ======== CHAEL f1 ======== UC1 13C P1 9.63 usec PLW1 103.00000000 W SFO1 125.7753932 MHz ======== CHAEL f2 ======== CPDPRG2 waltz16 UC2 1H PCPD2 80.00 usec PLW2 15.30000019 W PLW12 0.33006001 W PLW13 0.21123999 W SFO2 500.1520006 MHz F2 - Processing parameters SI 32768 SF 125.7628069 MHz WDW EM SSB 0 LB 3.00 Hz GB 0 PC 1.40 23.745 28.632 40.833 41.582 56.069 76.905 77.159 77.413 80.033 100.142 107.316 111.328 111.548 126.083 131.128 132.655 133.237 154.173 155.396 Boc MeO Lab SB sb-sg-1728 iitm_carbonshort CDCl3 /opt/topspin iitm 2 H 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm 13 C MR spectra of compound 14 S104

Current Data Parameters AME sb50712 EXPO 44 PROCO 1 F2 - Acquisition Parameters Date_ 20120707 Time 17.23 ISTRUM spect PROBHD 5 mm PABBO BB/ PULPROG deptsp135 TD 16384 SOLVET CDCl3 S 1000 DS 4 SWH 20161.291 Hz FIDRES 1.230548 Hz AQ 0.4063732 sec RG 202.34 DW 24.800 usec DE 6.50 usec TE 299.7 K CST2 130.0000000 D1 1.00000000 sec D2 0.00384615 sec D12 0.00002000 sec TD0 1 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm ======== CHAEL f1 ======== UC1 13C P1 9.63 usec P13 2000.00 usec PLW0 0 W PLW1 103.00000000 W SFO1 125.7728780 MHz SPAM5 Crp60comp.4 SPOAL5 0.500 SPOFFS5 0 Hz SPW5 14.59399986 W ======== CHAEL f2 ======== CPDPRG2 waltz16 UC2 1H P3 11.75 usec P4 23.50 usec PCPD2 80.00 usec PLW2 15.30000019 W PLW12 0.33006001 W SFO2 500.1515995 MHz F2 - Processing parameters SI 32768 SF 125.7628180 MHz WDW EM SSB 0 LB 3.00 Hz GB 0 PC 1.40 23.614 28.546 40.725 41.491 55.972 Boc MeO 100.031 111.232 111.468 H Lab SB sb/sg/1728 iitm_c13dept135 CDCl3 /opt/topspin iitm 15 13 C DEPT MR spectrum of indole derivative 14 S105

Lab SB sb-sg-1728 COSYGPSW CDCl3 /opt/topspin iitm 2 ppm 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 Current Data Parameters AME sb50712 EXPO 50 PROCO 1 F2 - Acquisition Parameters Date_ 20120708 Time 18.57 ISTRUM spect PROBHD 5 mm PABBO BB/ PULPROG cosygpppqf TD 2048 SOLVET CDCl3 S 1 DS 8 SWH 4672.897 Hz FIDRES 2.281688 Hz AQ 0.2191860 sec RG 19.19 DW 107.000 usec DE 6.50 usec TE 297.4 K D0 0.00000300 sec D1 1.93405402 sec D11 0.03000000 sec D12 0.00002000 sec D13 0.00000400 sec D16 0.00020000 sec I0 0.00021400 sec ======== CHAEL f1 ======== UC1 1H P0 11.75 usec P1 11.75 usec P17 2500.00 usec PLW1 15.30000019 W PLW10 3.12479997 W SFO1 500.1522013 MHz ====== GRADIET CHAEL ===== GPAM1 SMSQ10.100 GPZ1 10.00 % P16 1000.00 usec F1 - Acquisition parameters TD 128 SFO1 500.1522 MHz FIDRES 36.507008 Hz SW 9.343 ppm FnMODE QF F2 - Processing parameters SI 1024 SF 500.1500000 MHz WDW QSIE SSB 0 LB 0 Hz GB 0 PC 1.40 F1 - Processing parameters SI 1024 MC2 QF SF 500.1500000 MHz WDW SSB 0 LB 0 Hz GB 0 Boc MeO H 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm 1 H 1 H COSY MR spectrum of indole derivative 14 S106

OH H Cl Cl 1 H MR spectrum of indole derivative 15 S107

S108 Expanded 1 H MR spectrum of indole derivative 15

OH H Cl Cl 13 C MR spectrum of indole derivative 15 S109

OH H 1 H MR spectrum of indole derivative 16 MeO S110

S111 Expanded 1 H MR spectrum of indole derivative 16

OH H MeO 13 C MR spectrum of indole derivative 16 S112

I MeO H 1 H MR spectrum of indole derivative 16A S113

S114 Expanded 1 H MR spectrum of indole derivative 16A

I H MeO 13 C MR spectrum of indole derivative 16A S115

3 MeO H 1 H MR spectrum of indole derivative 16B S116

S117 Expanded 1 H MR spectrum of indole derivative 16B

3 H MeO 13 C MR spectrum of indole derivative 16B S118

H 3 C O 1 H MR spectrum of indole derivative IV H H MeO S119

S120 Expanded 1 H MR spectrum of indole derivative IV

H 3 C H O H 13 C MR spectrum of indole derivative IV MeO S121

13 C DEPT MR spectrum of indole derivative IV H 3 C O H H MeO S122

H 3 C O H MeO H 1 H 1 H COSY MR spectrum of indole derivative IV S123

Me Me H 1 H MR spectrum of indole derivative 17 S124

S125 Expanded 1 H MR spectrum of indole derivative 17

Me H Me 13 C MR spectrum of indole derivative 17 S126

Me Me H 13 C DEPT MR spectrum of indole derivative 17 S127

Me H 1 H 1 H COSY MR spectrum of indole derivative 17 Me S128