Supporting Information

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1 Supporting Information [Cp*IrCl 2 ] 2 catalysed indirect functionalisation of alcohols: ovel strategies for the synthesis of substituted indoles Simon Whitney, Ronald Grigg *, Andrew Derrick and Ann Keep University of Leeds, Leeds, LS2 9JT. Pfizer Ltd., Chemical Research and Development, Ramsgate Road, Sandwich, Kent, CT13 9J. Johnson Matthey, Orchard Road, Royston, ertfordshire, SG8 5E. R.Grigg@leeds.ac.uk COTETS Part I. Experimental section S-2 General Procedures S-3 Compound Data S-3 References S-13 Part II. 1 MR Spectra S-15 S-1

2 Experimental section: 1 -MR were recorded on a Bruker Avance instrument operating at 500 Mz, 13 C-MR spectra were recorded on a Bruker DPX300 at 75.5 Mz. Chemical shifts () are given in parts per million (ppm) downfield relative to tetramethylsilane (TMS). Coupling constants are corrected and given in hertz (z). Unless otherwise stated deuteriochloroform (CDCl 3 ) was used as solvent. In assignment of the 1 -MR spectra, multiplicities and abbreviations used are as follows; Ar = aromatic, s = singlet, d = doublet, t = triplet, q = quartet, dd = doublet of doublets, dt = doublet of triplets, td = triplet of doublets, m = multiplet and br = broad. Mass spectra were recorded using a Micromass ZMD 2000 electrospray (ES) spectrometer and on a GCT Premier mass spectrometer employing electron impact ionisation (EI). Melting points were determined on a Griffin hot-stage apparatus and are uncorrected. Infrared spectroscopy was recorded using a Perkin-Elmer Spectrum One FT-IR spectrometer either as a thin film on sodium chloride plates. Thin films were prepared by the evaporation of a solution of the compound in chloroform. Flash column chromatography was performed using FluoroChem 60 (40-60 µm mesh) silica. Microanalyses were obtained using a Carlo Erba 1108 Elemental Analyser. The catalyst, [Cp*IrCl 2 ] 2 was prepared according to the literature method. 1 The primary alcohols, indoles and 2-amino/2-nitrophenyl ethyl alcohol were commercially available and used without further purification. 2-Amino-6-chlorophenethyl alcohol, 2 2-amino-5-methoxyphenethyl alcohol 2 and 1-(2-aminophenyl)-2-propanol 3 were prepared according to the literature methods. S-2

3 General procedure A Alkylation of indoles with primary alcohols A mixture of the indole (1.0 mmol), [Cp*IrCl 2 ] 2 (0.020 g, 2.5 mol %), KO (0.011 g, 0.2 mmol) and the alcohol (3.0 mmol) were combined in a thick walled glass tube. The tube was sealed with a rubber septum and purged with nitrogen and the mixture was magnetically stirred at 110 o C with conventional heating for 24 h then allowed to cool to room temperature. The reaction mixture was analysed by proton MR and thereafter purified with column chromatography. General procedure B One-pot synthesis of substituted indoles from 2-aminophenyl ethyl alcohols and primary alcohols Prepared as for general procedure A from amino alcohol (1.0 mmol), [Cp*IrCl 2 ] 2 (0.020g, 2.5 mol %), KO (0.112 g, 2.0 mmol) and the alcohol (5.0 mmol). Purification as for general procedure A. 3-Benzyl-1-indole. 4 Prepared according to general procedure A from indole (0.117 g, 1.0 mmol) and benzyl alcohol (0.324 g, 3.0 mmol) and by general procedure B from 2-aminophenyl ethyl alcohol (0.137 g, 1.0 mmol) and benzyl alcohol (0.540 g, 5.0 mmol). Silica gel chromatography eluting with 9:1 v/v hexane - ethyl acetate followed by crystallisation from DCM-hexane gave the product (0.166 g, 80%) by general procedure A and (0.161 g, 78%) by general procedure B. Also prepared from 2-nitrophenyl ethyl alcohol and benzyl alcohol: 2-itrophenyl ethyl alcohol (0.167 g, 1.0 mmol) and benzyl alcohol (1.080g, 10.0 mmol) were combined with [Cp*IrCl 2 ] 2 (0.020 g, 2.5 mol) and KO (0.112 g, 2.0 mmol) in a CEM microwave tube. The reaction vessel was sealed with a rubber septum and purged with nitrogen. The reaction mixture was magnetically stirred S-3

4 at 120 o C with conventional heating for 48 h and then allowed to cool to room temperature. The reaction mixture was analysed by proton MR and thereafter transferred with a small quantity of DCM for silica gel chromatography eluting with 9:1 v/v hexane-ethyl acetate followed by crystallisation from DCM-hexane gave the product (0.101 g, 49 %) as colourless plates. m.p o C, (lit m.p o C); (500 Mz, CDCl 3 ): 7.92 (br s, 1, ), 7.52 (d, 1, J 8.1, Ar), 7.35 (d, 1, J 8.1, Ar), (m, 4, 4 Ar), (m, 2, 2 Ar), 7.08 (t, 1, J 8.1, Ar), 6.90 (d, 1, J 1.7, Ar), 4.12 (s, 2, C 2 ); max /cm -1 (film) 3400, 1491, 1457, 1088, 757, 743, 710, 486;.R.M.S [ES+] found M C requires (Furan-2-ylmethyl)-1-indole. Prepared according to general procedure A from indole g (1.0 mmol) and furfuryl alcohol (0.294 g, 3.0 mmol). Silica gel chromatography eluting with 7:1 v/v hexane-ethyl acetate followed by crystallisation from DCM-hexane gave the product (0.166 g, 84%) as colourless plates. m.p o C; (500 Mz, CDCl 3,): 7.97 (br s, 1, ), 7.57 (d, 1, J 7.7, Ar), 7.36 (d, 1, J 8.1, Ar), 7.32 (d, 1, J 0.9, Ar), 7.19 (appar t, 1, J 7.3, Ar), 7.10 (appar t, 1, J 7.0, Ar), 7.06 (d, 1, J 2.1, Ar), 6.28 (appar t, 1, J 2.4, Ar), 6.02 (d, 1, J 2.6, Ar), 4.12 (s, 2, C 2 ). C (75 Mz, CDCl 3 ); (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (C 2 ).; max /cm -1 (film) 3415 (), 1503, 1456, 1418, 1352, 1338, 1223, 1008;.R.M.S [ES+] found M+a C Oa requires O S-4

5 3-(Thiophen-2-ylmethyl)-1-indole. Prepared according to general procedure A from indole (0.117 g, 1.0 mmol) and thiophene-2-methanol (0.342 g, 3.0 mmol). Silica gel chromatography eluting with 7:1 v/v hexane-ethyl acetate followed by crystallisation from DCM-hexane gave the product (0.115 g, 53%) as colourless plates. m.p o C. (Found: C, 72.95;, 5.15;, 6.45; S, 14.75: C S requires: C, 73.20;, 5.20;, 6.57; S, 15.03%); (500 Mz, CDCl 3 ); 7.97 (br s, 1, ), 7.56 (d, 1, J 7.7, Ar), 7.37 (d, 1, J 8.1, Ar), 7.20 (appar t, 1, J 7.5, Ar), 7.12 (d, 1, J 4.7, Ar), 7.10 (appar t, 1, J 7.5, Ar), 7.05 (d, 1, J 2.1, Ar), 6.91 (dd, 1, J 3.4, 4.7, Ar), 6.87 (d, 1, J 3.4, Ar), 4.31 (s, 2, C 2 ); C (75 Mz, CDCl 3 ); (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (C 2 ); max /cm -1 (film) 3392 (), 2886, 2832, 1439, 1088, 1033, 808, 751;.R.M.S. [EI+] found C S requires S 3-(Pyridin-3-ylmethyl)-1-indole. 5 Prepared according to general procedure A from indole (0.117 g, 1.0 mmol) and pyridine- 3-methanol (0.327 g, 3.0 mmol) and by general procedure B from 2-aminophenylethyl alcohol (0.137 g, 1.0 mmol) and 3-pyridinemethanol (0.546 g, 5.0 mmol) with heating for 48 h at 110 o C. Silica gel chromatography eluting with v/v 98:2 DCM-methanol followed by crystallisation from DCM- hexane gave the product (0.173 g, 83%) by general procedure A and (0.141 g, 68%) by general procedure B, as colourless micro needles. m.p o C, (lit m.p o C); (500 Mz, CDCl 3 ): 8.60 (s, 1, Ar), 8.45 (d, 1, J 4.3, Ar), 8.23 (br s, 1, ), 7.54 (d, 1, J 7.7, Ar), 7.48 (d, 1, J 7.7, Ar), 7.36 (d, 1, J 8.1, Ar), (m, 2, 2 Ar), 7.08 (appar t, 1, J 7.3, Ar), 6.92 S-5

6 (s, 1, Ar), 4.11 (s, 2, C 2 ); C (75 Mz, CDCl 3 ); (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (C 2 ); max /cm -1 (film) 3411 (), 2918, 1577, 1478, 1456, 1424, 1339, 1232;.R.M.S. [ES+] found M C requires (3,4-Dimethoxybenzyl)-1-indole. OMe OMe Prepared according to general procedure A from indole (0.117 g, 1.0 mmol) and 3,4- dimethoxy benzyl alcohol (0.504 g, 3.0 mmol). Silica gel chromatography eluting with 7:1 v/v hexane-ethyl acetate followed by crystallisation from DCM-hexane gave the product (0.187 g, 70%) as pale yellow prisms; m.p o C; (500 Mz, CDCl 3 ); 7.96 (br s, 1, ), 7.53 (d, 1, J 7.7, Ar), 7.34 (d, 1, J 8.1, Ar), 7.18 (appar t, 1, J 7.3, Ar), 7.08 (appar t, 1, J 7.5, Ar), 6.88 (d, 1, J 1.8, Ar), 6.83 (s, 1, Ar), 6.82 (d, 1, J 8.6, Ar), 6.78 (d, 1, J 8.6, Ar), 4.06 (s, 2, C 2 ), 3.85 (s, 3, OC 3 ), 3.81 (s, 3, OC 3 ).; C (75 Mz, CDCl 3 ); (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (C 3 ), (C 3 ), (C 2 ).; max /cm -1 (film) 3369 (), 3055, 2834, 1591, 1513, 1456, 1338, 1260;.R.M.S [ES+] found M+a C O 2 a requires (Benzo[d][1,3]dioxol-5-ylmethyl)-1-indole. Prepared by general procedure A from indole (0.117 g, 1.0 mmol) and 3,4- methylenedioxybenzyl alcohol (0.456 g, 3.0 mmol) and by general procedure B from O O S-6

7 2-aminophenyl ethyl alcohol (0.137 g, 1.0 mmol) and 3,4-methylenedioxybenzyl alcohol (0.760 g, 5.0 mmol). Silica gel chromatography eluting with 9:1 v/v hexane-ethyl acetate followed by crystallisation from DCM-hexane gave the product (0.196 g, 78%) by general procedure A and (0.178 g, 71%) by general procedure B, as colourless plates, m.p o C; (Found: C, 76.40;, 5.15;, 5.50: C O 2 requires: C, 76.48;, 5.21;, 5.57%); (500 Mz, CDCl 3 ): 7.90 (br s, 1, ), 7.50 (d, 1, J 8.0, Ar), 7.33 (d, 1, J 8.0, Ar), 7.18 (appar t, 1, J 8.0, Ar), 7.07 (appar t, 1, J 8.0, Ar), 6.91 (d, 1, J 2.4, Ar), (m, 3, 3 Ar), 5.88 (s, 2, OC 2 O), 4.02 (s, 2, C 2 ).; C (75 Mz, CDCl 3 ): (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (OC 2 O), (C 2 ).; max /cm -1 (film) 3417 (), 3055, 2853, 1500, 1487;.R.M.S [ES+] found M C O 2 requires (4-Methoxybenzyl)-1-indole. OMe Prepared according to general procedure B from 2-aminophenyl ethyl alcohol (0.137 g, 1.0 mmol) and 3-(4-methoxy benzyl) alcohol (0.690 g, 5.0 mmol). Silica gel chromatography eluting with DCM followed by crystallisation from DCM-hexane gave the product (0.176 g, 75%) as colourless micro needles, m.p o C; (Found: C, 80.00;, 6.30;, 5.85%; C O requires: C, 80.98;, 6.37;, 5.90%); (500 Mz, CDCl 3 ): 7.91 (brs, 1, ), 7.51 (d, 1, J 8.0, Ar), 7.34 (d, 1, J 8.1, Ar), 7.20 (d, 2, J 8.8, 2 Ar), 7.18 (appar t, 1, J 8.0, Ar), 7.07 (appar t, 1, J 8.0, Ar), 6.89 (d, 1, J 2.4, Ar), 6.82 (d, 2, J 8.8, 2 Ar), 4.05 (s, 2, C 2 ), 3.77 (s, 3, OC 3 ); C (75 Mz, CDCl 3 ): (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (C 3 ), (C 2 ); max /cm -1 (film) 3412 (), 2902, 2833, 1610, 1509, 1455, 1338, 1299; RMS [ES+] found M C O requires S-7

8 3-(4-Chlorobenzyl)-1-indole. Prepared according to general procedure A from indole (0.117 g, 1.0 mmol) and 4- chlorobenzyl alcohol (0.426 g, 3.0 mmol) with heating for 48 h and by general procedure B from 2-aminophenylethyl alcohol (0.137 g, 1.0 mmol) and 4-chlorobenzyl alcohol (0.710 g, 5.0 mmol) with heating at 110 o C for 48 h. Silica gel chromatography eluting with 7:1 v/v hexane-ethyl acetate followed by crystallisation from DCM-hexane gave the product (0.195 g, 81%) by general procedure A and (0.163 g, 68%) by general procedure B as colourless needles. m.p o C. (500 Mz, CDCl 3 ): 7.94 (br s, 1, ), 7.46 (d, 1, J 7.7, Ar), 7.36 (d, 1, J 8.1, Ar), (m, 5, 5 Ar), 7.08 (t, 1, J 7.5, Ar), 6.91 (s, 1, Ar), 4.08 (s, 2, C 2 ).; C (500 Mz, CDCl 3 ): (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (C 2 ).; max /cm -1 (film) 3416 (), 3056, 2921, 1617, 1488, 1455;.R.M.S [EI-] found M-1. C Cl requires Cl 3-(3,5-Difluorobenzyl)-1-indole. F Prepared according to general procedure B from 2-aminophenylethyl alcohol (0.137 g, 1.0 mmol) and 3,5-difluorobenzyl alcohol (0.720 g, 5.0 mmol) with heating at 110 o C for 48 h. Silica gel chromatography eluting with 7:1 v/v hexane-ethyl acetate followed by crystallisation from DCM-hexane gave the product (0.185 g, 71%) as colourless plates. m.p o C; (Found: C, 73.80;, 4.60;, 5.75; F, 15.80; C F 2 requires: C,74.06;, 4.56;, 5.76; F, 15.62%); (500 Mz, CDCl 3 ); 8.00 (br s, 1, ), 7.45 (d, 1, J 7.7, Ar), 7.37 (d, 1, J 8.1, Ar), 7.20 (appar t, 1, J 7.3, Ar), 7.09 (appar t, 1, J 7.3, Ar), 6.99 (s, 1, Ar), 6.78 (d, 2, 3 J F 6.4, Ar), 6.62 (t, 1, 3 J F 9.0, Ar), 4.09 (s, 2, C 2 ); C (75 Mz, CDCl 3 ): (dd, 1&3 J CF 247.6, 12.8, 2 CF), F S-8

9 (t, 2 J CF 8.7, ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (dd, 2&4 J CF 9.8, 7.2, 2 ArC), (ArC), (t, 2 J CF 25.7, ArC), (C 2 ); max /cm -1 (film) 3416 (), 2906, 1625, 1593, 1456, 1324, 1115, 989;.R.M.S. [EI+] found M C F 2 requires Isobutyl-1-indole. 6 Prepared by general procedure A from indole (0.117 g, 1.0 mmol) and 2-methylpropanol (0.222 g, 3.0 mmol) with heating for 48 h at 110 o C and by general procedure B from 2- aminophenyl ethyl alcohol (0.137 g, 1.0 mmol) and 2-methylpropanol (0.370 g, 5.0 mmol) with heating for 48 h at 110 o C. Silica gel chromatography eluting with 4:1 v/v DCM- hexane gave the product (0.061 g, 35%) by general procedure A and (0.091 g, 53%) by general procedure B as a pale amorphous solid; m.p o C (lit o C); (500 Mz, CDCl 3 ); 7.87 (br s, 1, ), 7.60 (d, 1, J 7.7, Ar), 7.34 (d, 1, J 8.1, Ar), 7.17 (appar t, 1, J 7.3, Ar), 7.10 (appar t, J 7.3, Ar), 6.90 (s, 1, Ar), 2.62 (d, 2, J 6.8, C 2 ), (m, 1, C), 0.95 (d, 6, J 6.8, 2 C 3 ); max (film)/cm , 2952, 2922, 1455, 1419, 1334, 1228, 740;.R.M.S [EI+] found M C requires Benzyl-5-methoxy-1-indole. 7 MeO Ph Prepared according to general procedure A from 5-methoxy indole (0.147 g, 1.0 mmol) and benzyl alcohol (0.324 g, 3.0 mmol) and by general procedure B from 2-amino-5- methoxyphenyl ethyl alcohol (0.167 g, 1.0 mmol) and benzyl alcohol (0.540 g, 5.0 S-9

10 mmol). Silica gel chromatography eluting with 1:1 v/v petroleum ether-diethyl ether followed by crystallisation from DCM-hexane gave the product (0.154 g, 65%) by general procedure A and (0.175 g, 74%) by general procedure B as colourless needles. m.p o C, (lit. m.p o C); (500 Mz, CDCl 3 ); 7.76 (br s, 1, ), (m, 4, 4 Ar), (m, 2, 2 Ar), 6.94 (d, 1, J 2.1, Ar), 6.83 (dd, 1, J 2.1, 8.8, Ar), 6.81 (d, 1, J 2.1, Ar), 4.06 (s, 2, C 2 ), 3.78 (s, 3, C 3 ).; max /cm -1 (film) 3420 (), 2901, 1625, 1583, 1484, 1452;.R.M.S [ES+] found M C O requires Methoxy-3-((5-methoxy-1-indol-3-yl)(phenyl)methyl)-1-indole. MeO OMe Prepared according to general procedure A from indole (0.147 g, 1.0 mmol) and benzyl alcohol (0.324 g, 3.0 mmol). Silica gel chromatography eluting with 1:1 v/v petroleum ether-diethyl ether gave the product (0.058 g, 30%) as a colourless solid. m.p o C; (500 Mz, CDCl 3 ); 7.80 (br s, 2, 2 ), 7.36 (d, 2, J 7.7, 2 Ar), (m, 5, 5 Ar), 6.82 (d, 2, J 9.0, 2 Ar), 6.79 (s, 2, 2 Ar), 6.65 (s, 2, 2 Ar), 5.77 (s, 1, C), 3.68 (s, 6, 2 OC 3 ); C (500 Mz, CDCl 3 ); (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (C 3 ), (C 2 ).; max /cm -1 (film) 3415 (), 2935, 1618, 1582, 1483, 1452;.R.M.S [ES+] found M C O 2 requires S-10

11 3-Benzyl-1-indole-5-carbonitrile. C Ph Prepared according to general procedure A from 5-cyano indole (0.142 g, 1.0 mmol) and benzyl alcohol (0.324 g, 3.0 mmol) with heating for 48 h. Silica gel chromatography eluting with 1:1 v/v petroleum ether-diethyl ether followed by crystallised from DCMhexane to give the product (0.139 g, 60%) as colourless micro needles. m.p o C.; (500 Mz, CDCl 3 ); 8.34 (br s, 1, ), 7.84 (s, 1, Ar), (m, 6, 6 Ar), 7.06 (d, 1, J 1.7, Ar), 4.10 (s, 2, C 2 ); C (500 Mz, CDCl 3 ); (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (C), (C 2 ); max /cm -1 (film) 3335 (), 2220 (C), 1618, 1494, 1471, 1453;.R.M.S [ES+] found M+a C a requires Benzyl-5-fluoro-1-indole. F Ph Prepared according to general procedure A from 5-fluoro indole (0.135 g, 1.0 mmol) and benzyl alcohol (0.324 g, 3.0 mmol). Silica gel chromatography eluting with 7:1 v/v hexane-ethyl acetate followed by crystallisation from DCM-hexane gave the product (0.164 g, 73%) as colourless prisms. m.p o C; (500 Mz, CDCl 3 ); 7.87 (br s, 1, ), (m, 6, 6 Ar), 7.13 (dd, 1, J 9.6, 2.1, Ar), 6.94 (s, 1, Ar), 6.91 (appar td, 1, J 9.0, 2.1, Ar), 4.05 (s, 2, C 2 ).; C (75 Mz, CDCl 3 ); (d, ArC, 1 J CF 234.1), (ArC), (ArC), (ArC), (ArC), (d, ArC, 3 J CF 9.8), (ArC), (ArC), (ArC), (d, ArC, 3 J CF 9.8), (d, ArC, 2 J CF 26.4), (d, ArC, 2 J CF 23.3), (C 2 ); max /cm -1 (film) 3408 (), 1624, 1577, 1483, 1448, 1188;.R.M.S [ES+] found M C F requires S-11

12 3-Benzyl-2-methyl-1-indole. 8 Prepared according to general procedure A from 2-methyl indole (0.131 g, 1.0 mmol) and benzyl alcohol (0.324 g, 3.0 mmol) and by general procedure B from 1-(2-aminophenyl)- 2-propanol (0.151 g, 5.0 mmol) and benzyl alcohol (0.540 g, 5.0 mmol). Silica gel chromatography eluting with 7:1 v/v hexane-ethyl acetate followed by crystallisation from DCM-hexane gave the product (0.153 g, 69%) by general procedure A and (0.157 g, 71%) by general procedure B, as colourless needles. m.p o C, (lit m.p o C); (500 Mz, CDCl 3 ); 7.65 (br s, 1, ), 7.38 (d, 1, J 7.7, Ar), (m, 5, 5 Ar), (m, 1, Ar), 7.09 (appar t, 1, J 7.5, Ar), 7.01 (appar t, 1, J 7.3, Ar), 4.05 (s, 2, C 2 ), 2.33 (s, 3, C 3 ).; max /cm -1 (film) 3410 (), 1687, 1610, 1462, 1391, 1301;.R.M.S [EI+] found M C requires Me Ph 2-(1-indol-3-yl)-,-dimethylethanamine. 9 Prepared according to general procedure B from 2-aminophenyl ethyl alcohol (0.137 g, 1.0 mmol) and 2-(dimethylamino)ethanol (0.446 g, 5.0 mmol) with heating for 48 h at 110 o C. Silica gel chromatography eluting with 94:1:5 v/v DCM-methanol-triethylamine gave the product (0.140 g, 74%) as a pale amorphous solid; m.p o C, (lit m.p o C); (500 Mz, CDCl 3 ); 8.30 (br s, 1, ), 7.61 (d, 1, J 7.7, Ar), 7.31 (d, 1, J 8.1, Ar), 7.17 (appar t, 1, J 7.3, Ar), 7.10 (appar t, 1, J 7.3, Ar), 6.96 (s, 1, Ar), 2.65 (t, 2, J 8.1, C 2 ), 2.65 (t, 2, J 8.1, C 2 ), 2.35 (s, 6, 2 C 3 ); max /cm -1 (film) 3414, 2924, 2823, 1456, 1354, 1232, 1009, 738;.R.M.S [ES+] found M C requires S-12

13 3-Benzyl-4-chloro-1-indole. Cl Prepared according to general procedure B from 2-amino,6-chlorophenyl ethyl alcohol (0.172 g, 1.0 mmol) and benzyl alcohol (0.540 g, 5.0 mmol). Silica gel chromatography eluting with 7:1 v/v hexane-ethyl acetate followed by crystallisation from DCM-hexane gave the product (0.157 g, 65%) as colourless needles. m.p o C; (Found: C, 74.3;, 5.00;, 5.69; Cl, 14.8; C Cl requires: C, 74.53;, 5.00;, 5.79; Cl, 14.67%); (500 Mz, CDCl 3 ); 7.93 (br s, 1, ), 7.52 (d, 1, J 8.0, Ar), 7.35 (d, 1, J 8.1, Ar), (m, 2, 2 Ar), 7.08 (appar t, 1, J 7.5, Ar), 6.91 (d, 1, J 1.7, Ar), 4.12 (s, 2, C 2 ); C (75 Mz, CDCl 3 ); (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (ArC), (C 2 ); max /cm -1 (film) 3417 (), 3025, 1600, 1493, 1454, 1337, 1223, 1089;.R.M.S. [ES+] found M+1-Cl C requires Ph References 1 Ball, R.G.; Graham, W.A.G.; einekey, D.M.; oyano, J.K.; McMaster, A.D.; Mattson, B.M.; Michel, S.T. Inorg. Chem. 1990, 29, Tsuji, Y.; Kotachi, S.; uh, K-T.; Watanabe, Y. J. Org. Chem. 1990, 55, Fujita, K.; Yamamoto, K.; Yamaguchi, R. Org. Lett. 2004, 4, Swaminathan, S.; Ranganathan, S.; Sulochana. J. Org. Chem. 1958, 23, Sainsbury, M.; Schinazi, R.F. J. Chem. Soc., Chem. Commun. 1975, 540. S-13

14 6 Szmuszkovivz, J. J. Org. Chem. 1962, 27, Macor, J.E.; Weher, J.M. eterocycles 1993, 35, Appleton, J.E.; Dack, K..; Green, A.D.; Steele, J. Tetrahedron Lett. 1993, 34, Grina, J.A.; Ratcliff, M.R.; Stermitz, F.R. J. Org. Chem. 1982, 47, S-14