Electronic Supplementary Information (ESI)

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry Electronic Supplementary Information (ESI) For Iron-Catalysed xidative Amidation of Alcohols with Amines Silvia Gaspa, a Andrea Porcheddu a and Lidia De Luca* a Dipartimento di Chimica e Farmacia, Università degli Studi di Sassari, Sassari, Italy Email: ldeluca@uniss.it S1

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 1. Experimental Procedures for Amides 4a-q and Product Characterization S3-7 2. References S8 3. MR Spectra of Compounds 4a-q S9-42 S2

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry Experimental Procedures General Information. All reagents and solvents were as obtained by commercial source. All the reactions were carried out under 2 atmosphere using standard techniques. Column chromatography was generally performed on silica gel (pore size 60 A, 40-63 mm particle size) and reactions were monitored by thin-layer chromatography (TLC) analysis was performed with Merck Kieselgel 60 F254 plates and visualized using UV light at 254 nm and KMn4 staining. 1H MR and 13C MR spectra were measured on a Bruker Avance III 400 spectrometer (400 MHz or 100 MHz, respectively) with CDCl3 as solvent and recordered in ppm relative to internal tetramethylsilane standard. The peak patterns are indicated as follows: s, singlet; d, doublet; t, triplet; m, multiplet; q, quartet; br, broad. The coupling constants, J, are reported in Hertz (Hz). The IR spectra were recorded on a Jasco FTIR-480 Plus Fourier Transform spectrometer. Melting points were determined in open capillary tubes and are uncorrected. High resolution mass spectroscopy data of the product were collected on a Waters Micromass GCT instrument. General procedures for amides 4a-q: An amine (0.32 mmol) was added to a solution of -chlorosuccinimide (0.352 mmol) in 10 ml of acetonitrile under 2 atmosphere and at room temperature. The reaction was monitored by TLC until disappearance of the amine (1-2 hours), then were added an alcohol (1.6 mmol), TBHP (1.6 mmol, 0.22 ml of a 70 wt% in water) and FeCl 3. 6H 2 (0.045 mmol) under 2 atmosphere. The resulting reaction mixture was heated in an oil bath at 85 C (the reaction was monitored by TLC until disappearance of - chloroamine). Then the reaction mixture was quenched with 20 ml of a saturated solution of a 2 S 3 (for removal of excess TBHP) and extracted three times with 40 ml of diethyl ether. The combined organic phases were dried over anhydrous a 2 S 4 and the solvent was evaporated under reduced pressure. The crude product was purified by silica gel column chromatography to provide the desired amides 4a-q. S3

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry Compound characterizations,-dibenzylbenzamide (4a). 1 Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-acet = 4.2/0.8), R f = 0.44, to afford a white solid in 96% yield (m.p. 113-115 C); 1 H MR (400 MHz, CDCl 3 ) δ 4.39 (s, 2H), 4.70 (s, 2H), 7.13-7.15 (m, 2H), 7.24-7.39 (m, 11H), 7.48-7.51 (m, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 46.8, 51.4, 126.7, 127.0, 127.5, 128.4, 128.5, 128.7, 129.6, 136.2, 172.2; IR (neat) ν = 3058, 3028, 2924, 1633, 1494, 1452, 1423, 1362, 1265, 1143, 1076, 1027, 991, 736, 700. Me,-dibenzyl-4-methoxybenzamide (4b). 12 Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-acet = 3.8/1.2), R f = 0.38, to afford a white solid in 74% yield (m.p. 119-121 C); 1 H MR (400 MHz, CDCl 3 ) δ 3.80 (s, 3H), 4.48 (br s, 2H), 4.67 br (s, 2H), 6.88 (d, J = 8.8 Hz, 2H), 7.2-7.38 (m, 10H), 7.48 (d, J = 8.5 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 44.1, 55.2, 60.3, 113.8, 126.9, 127.5, 128.2, 128.5, 128.7, 136.9, 160.2, 172.2; IR (neat) ν = 3062, 2924, 2853, 1629, 1513, 1494, 1421, 1363, 1265, 1176, 1030, 993, 738, 701.,-dibutyl-2-methylbenzamide (4c). Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-acet = 4/1), R f = 0.51, to afford a pale yellow oil in 76% yield; 1 H MR (400 MHz, CDCl 3 ) δ 0.74 (t, J = 7.2 Hz, 2H), 0.98 (t, J = 7.4 Hz, 2H), 1.1 (q, J = 7.4 Hz, 2H), 1.37-1.47 (m, 4H), 1.6-1.7 (m, 2H), 2.28 (s, 3H), 3.04 (t, J = 7.4 Hz, 2H), 3.3 (br s, 2H), 3.65 ( br s, 2H), 7.12-7.25 (m, 4H); 13 C MR (100 MHz, CDCl 3 ) δ 13.7, 14.1, 19.1, 19.9, 20.6, 29.8, 30.8, 44.2, 48.2, 125.8, 125.9, 128.6, 130.4, 134.1, 137.4, 171.4; IR (neat) ν = 2958, 2931, 2869, 1633, 1463, 1423, 1376, 1301, 1261, 746. HRMS (EI) ([M + ]) Calcd. For C 16 H 25 : 247.1936, Found: 247.1933. morpholino(o-tolyl)methanone (4d). 2 Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-acet = 2.5/2.5), R f = 0.31, to afford a yellow oil in 86% yield; 1 H MR (400 MHz, CDCl 3 ) δ 2.32 (s, 3H), 3,24 (br d, J = 4,5 Hz, 2H), 3.57 (br t, J = 4.5 Hz, 2H), 3.76-3.84 (br m, 4H), 7.14-7.3 (m, 4H); 13 C MR (100 MHz, CDCl 3 ) δ 19.1, 41.9, 47.3, 66.9, 67.0, 125.8, 126.0, 129.1, 130.5, 134.2, 135.6, 170.1; IR (neat) ν = 3054, 2983, 2923, 2859, 1633, 1431, 1265, 1157, 704. 2 morpholino(4-nitrophenyl)methanone (4e). 2 Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-acet = 2.5/2.5), R f = 0.23, to afford a white solid in 77% yield (m.p. 98-101 C); 1 H MR (400 MHz, CDCl 3 ) δ 3.41-3.82 (br m, 8H), 7.61 (d, J = 8.8 Hz, 2H), 8.31 (d, J = 8.8 Hz, 2H); 13 C MR (100 MHz, S4

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry CDCl 3 ) δ 42.6, 48.0, 66.8, 124.0, 128.2, 141.4, 148.5, 168.1; IR (neat) ν = 2922, 2856, 1637, 1523, 1435, 1352, 1279, 1113, 1012, 895, 839, 735. F (4-fluorophenyl)(piperidin-1-yl)methanone (4f). 3 Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-acet = 3/2), R f = 0.2, to afford a pale yellow oil in 70% yield; 1 H MR (400 MHz, CDCl 3 ) δ 1.57 (br s, 2H), 1.71 (br s,4h), 3.37 (br s, 2H), 3.71 (br s, 2H), 7.08-7.12 (m, 2H), 7.39-7.43 (m, 2H), 13 C MR (100 MHz, CDCl 3 ) δ 24.6, 25.7, 26.6, 43.2, 48.9, 115.3, 115.6, 129.0, 129.1, 132.4, 132.5, 161.9, 164.4, 169.4; IR (neat) ν = 2942, 1628, 1442, 1265, 1157, 1004, 847, 739. Cl (4-chlorophenyl)(piperidin-1-yl)methanone (4g). 3 Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-et 2 = 3/2), R f = 0.2, to afford a white solid in 69% yield (m.p. 59-61 C); 1 H MR (400 MHz, CDCl 3 ) δ 1.54 (br, s, 2H), 1.70 (br s, 4H), 3.35 (br s, 2H), 3.71 (br s, 2H), 7.34-7.41 (m, 4H); 13 C MR (100 MHz, CDCl 3 ) δ 24.5, 25.6, 26.6, 43.2, 48.9, 128.4, 128.7, 134.8, 135.4, 169.2; IR (neat) ν = 2937, 1629, 1440, 1277, 1090, 1003, 737. Br (4-bromophenyl)(piperidin-1-yl)methanone (4h). 4 Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-et 2 = 3/2), R f = 0.23, to afford a white solid in 80% yield (m.p. 75-78 C); 1 H MR (400 MHz, CDCl 3 ) δ 1.54 (br s, 2H), 1.70 (br s, 4H), 3.26 (br s, 2H), 3.71 (br s, 2H), 7.29 (d, J = 8.5 Hz, 2H), 7.55 (d, J = 8.5 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 24.5, 25.6, 26.5, 43.3, 48.8, 123.6, 128.6, 131.6, 135.3, 169.3; IR (neat) ν = 2933, 2854, 1631,1441, 1277, 1111, 1068, 1001, 833, 733. Cl (3-chlorophenyl)(piperidin-1-yl)methanone (4i). 5 Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-acet = 3.8/1.2), R f = 0.45, to afford a yellow oil in 58% yield; 1 H MR (400 MHz, CDCl 3 ) δ 1.55 (br s, 4H),1.71 (br s, 4H), 3.35 (br s, 2H), 3.72 (br s, 2H), 7.27-7.40 (m, 4H); 13 C MR (100 MHz, CDCl 3 ) δ 24.5, 25.6, 26.6, 43.2, 48.8, 124.9, 127.0, 129.5, 129.8, 134.5, 138.2, 168.7; IR (neat) n = 2931, 2856, 1631, 1566, 1439, 1280, 800, 739. -benzyl--methylbenzamide (4j). 4 Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-et 2 = 3.5/1.5), R f =0.26,to afford a pale yellow oil in 79% yield; 1 H MR (400 MHz, CDCl 3 ) δ 2.89 (br s, 1.5H), 3.06 (br s, 1.5H), 4.54 (br s, 1H), 4.79 (br s, 1H), 7.20-7.47 (m, 10H); 13 C MR (100 MHz, CDCl 3 ) δ 33.2, 37.1, 50.8, 55.2, 126.8, 127.0, 127.6, 127.9, 128.2, 128.4, 128.8, 129.6, 136.3, 136.6, 137.1, 170.8, 171.6; IR (neat) ν = 2921, 1631, 1450, 1400, 1265, 1070, 1026, 698. S5

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry S,-dibenzylthiophene-2-carboxamide (4k). 1 Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-et 2 = 3/2), R f = 0.58, to afford a white solid in 98% yield (m.p. 47-50 C); 1 H MR (400 MHz, CDCl 3 ) δ 4.75 (s, 4H), 6.98 (dd, J = 3.7 Hz, J = 5.1Hz, 1H), 7.30-7.42 (m, 11H), 7.47 (dd, J = 1.2 Hz, J = 5.1Hz, 1H); 13 C MR (100 MHz, CDCl 3 ) δ 50.1, 126.9, 127.6, 128.6, 128.8, 129.3, 136.6, 137.7, 165.1. IR (neat) ν = 3062, 3004, 2978, 2954, 2914, 1611, 1583, 1519, 1494, 1453, 1422, 1364, 1347, 1306, 1250, 1078, 889. piperidin-1-yl(o-tolyl)methanone (4l). 6 Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-acet = 3.5/1.5), R f = 0.38, to afford a pale yellow oil in 85% yield; 1 H MR (400 MHz, CDCl 3 ) δ 1.46 (s, 2H), 1.66 (s, 4H), 2.31 (s, 3H), 3.17 (d, J = 4.1 Hz, 2H), 3.71 (br s, 1H), 3.79 (br s, 1H), 7.21 (m, 4H); 13 C MR (100 MHz, CDCl 3 ) δ 18.9, 24.5, 25.7, 26.5, 42.3, 47.8, 125.6, 125.8, 128.5, 130.2, 134.0, 136.7, 169.8; IR (neat) ν = 3049, 2938, 2857, 1627, 1444, 1350, 1288, 1271, 1240, 1129, 1097, 1027, 1000, 733, 700, 665. S H -benzylthiophene-2-carboxamide (4m). 7 Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-et 2 = 2.5/2.5), R f =0.35, to afford a pale yellow oil in 63% yield; 1 H MR (400 MHz, CDCl 3 ) δ 4.64 (d, J = 5.7Hz, 2H), 6.35 (br s, 1H), 7.09 (dd,, J = 3.7 Hz, J = 5.1Hz, 1H), 7.31-7.35 (m, 1H), 7.37-7.38 (m, 4H), 7.50 (dd,, J = 1.2 Hz, J = 5.1Hz, 1H), 7.53 (dd,, J = 1.1 Hz, J = 2.5Hz, 1H); 13 C MR (100 MHz, CDCl 3 ) δ 44.0, 127.6, 127.7, 127.9, 128.1, 128.8, 130.0, 138.0, 138.7, 161.8; IR (neat) ν = 2922, 1629, 1545, 1421, 1265, 737. H -pentylbenzamide (4n). 8 Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-et 2 = 2.5/2.5), R f =0.51,to afford a pale yellow oil in 92% yield; 1 H MR (400 MHz, CDCl 3 ) δ 0.94 (t, J = 7.1Hz, 3H), 1.38 (m, 4H), 1.64 (t, J = 7.3Hz, 2H), 3.47 (q, J = 7.2 Hz, 2H), 6.19 (br s, 1H), 7.42-7.53 (m, 3H), 7.78 (m, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 14.0, 22.4, 29.1, 29.4, 40.1, 126.8, 128.5, 131.3, 134.9, 167.5; IR (neat) ν = 3064, 2956, 2929, 2860, 1639, 1576, 1545, 1491, 1464, 1375, 1309, 1209, 1153, 1074, 1028, 928, 877, 804, 698. H -heptylbiphenyl-4-carboxamide (4o). Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-acet = 4/1), R f =0.39,to afford a pale yellow oil in 72% yield; 1 H MR (400 MHz, CDCl 3 ) δ 0.91 (t, J = 6.9 Hz, 3H), 1.28-1.42 (m, 8H), 1.63-1.70 (m, 2H), 3.50 (q, J = 6.9 Hz, 2H), 6.18 (br s, 1H), 7.41 (t, J = 7.3 Hz, 1H), 7.49 (t, J = 7.7Hz, 2H), 7.62-7.69 (m, 4H), 7.85 (d, J = 8.5Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 14.1, 22.6, 27.0, 29.0, 29.7, 31.8, 40.1, 127.1, 127.2, 127.3, 127.9, 128.9, 133.5, 140.1, 144.1, 167.2; ; IR (neat) ν = 3041, 2922, 2852, 1630, 1537, 1469, 1265, 850, 740; HRMS (EI) ([M + ]) Calcd. For C 20 H 25 : 295.1936, Found: 295.1938. H -butylnaphthalene-2-carboxamide (4p). 9 Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-et 2 = 3/2), R f = 0.25, to afford a white solid in 81% yield (m.p. 98-101 C); 1 H MR (400 MHz, CDCl 3 ) δ 1.01 (t, J = 7.3 Hz, 3H), 1.44-1.53 (m, 2H), 1.64-1.71 (m, 2H), 3.57 (q, J =8.4 Hz, 2H), 6.00 (br s, 1H), S6

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 7.45-7.49 (m, 1H), 7.52-7.61 (m, 3H), 7.88-7.94 (m, 2H), 8.31 (d, J = 8.3 Hz, 1H); 13 C MR (100 MHz, CDCl 3 ) δ 13.8, 20.2, 31.8, 39.8, 124.7, 125.4, 126.4, 127.1, 128.3, 130.1, 133.7, 134.9, 169.5. IR (neat) ν = 3051, 2927, 1637, 1539, 1460, 1304, 1257, 1151, 1020, 779, 734. H methyl 4-(phenethylcarbamoyl)benzoate (4q). Prepared according to the general procedure. The product was purified by flash chromatography on silica gel (v/v petroleum ether-et 2 = 2/3), R f =0.34, to afford a white solid in 98% yield (m.p. 141-145 C); 1 H MR (400 MHz, CDCl 3 ) δ 2.97 (t,, J = 6.8 Hz, 2H), 3.76 (q,, J = 6.2 Hz, 2H), 3.95 (s, 3H), 6.23 (br s, 1H), 7.25-7.38 (m, 5H), 7.76 (d, J = 8.3 Hz, 2H), 8.09 (d, J = 8.3 Hz, 2H); 13 C MR (100 MHz, CDCl 3 ) δ 35.6, 41.2, 52.4, 126.7, 126.9, 128.7, 128.8, 129.8, 132.7, 138.5, 138.7, 166.3, 166.6. IR (neat) ν = 3327, 2923, 1720, 1635, 1543, 1439, 1280, 1196, 1157, 1113, 870, 821, 739, 698; HRMS (EI) ([M + ]) Calcd. For C 17 H 17 3 : 283.1208, Found: 283.1211. S7

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry References 1 2 3 4 5 6 7 8 9 R. Cadoni, A. Porcheddu, G. Giacomelli and L. De Luca, rg. Lett., 2012, 14, 5014. T. T. Dang, Z. Yinghuai, S. C. Ghosh, C. Anqi, C. L. L. Chai and A. M. Seayad, Chem. Commun., 2012, 48, 1805. J. Li, F. Xu, Y. Zhang and Q. Shen, J. rg. Chem., 2009, 74, 2575. G.-L. Li, K. K.-Y. Kung and M.-K. Wong, Chem. Commun., 2012, 48, 4112. I. E. Pop, B. P. Déprez and A. L. Tartar, J. rg. Chem., 1997, 62, 2594. A. Porcheddu and L. De Luca, Adv. Synth. Cat. 2012, 354, 2949.. Gernigon, R. M. Al-Zoubi and D. G. Hall, J. rg. Chem., 2012, 77, 8386. M. Mori and Y. Ban, Chem. arm. Bull., 1976, 24, 1992. K. R. Reddy, C. U. Maheswari, M. Venkateshwar and M. L. Kantam, Eur. J. rg. Chem., 2008, 21, 3619. S8

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 7.513 7.481 7.385 7.244 7.147 7.128 4.702 4.398 4a 10.810.8 2.05 2.05 1.831.83 1.94 1.94 2 2 S9 ppm-14.668 10ppm 910 89 78 67 56 45 34 23 12 0

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 172.192 136.162 129.580 128.718 128.490 128.358 127.548 127.024 126.672 51.452 46.792 4a S10 0 200ppm-218.761 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 7.496 7.466 7.381 7.204 6.893 6.864 4.665 4.483 3.802 Me 4b 1.91 10.1 10.1 1.91 2.07 2.07 4.01 3 3 S11 10ppm-14.668 910 89 78 67 56 45 34 23 12 01

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 172.120 160.720 136.878 128.705 128.486 128.204 127.461 126.954 113.757 60.311 55.253 44.060 Me 4b S12 0 200ppm-218.761 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 7.262 3.648 3.298 2.278 1.655 1.444 1.368 1.135 1.060 0.980 0.751 4c 4.29 4.29 2.06 1.9 1.9 3 3 4.18 4.183.373.37 3.03 2.132.132.1 2.1 3.03 S13 ppm-14.668 10ppm 910 89 78 67 56 45 34 23 12 0

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 171.386 137.437 134.063 130.417 128.643 125.972 125.853 48.231 44.233 30.810 29.804 20.591 19.968 19.102 14.105 13.741 4c S14 0 200ppm-218.761 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 7.304 7.146 3.841 3.818 3.783 3.760 3.585 3.576 3.566 3.245 3.234 2.319 2.07 2.272.27 2.07 2.97 2.97 44 2.132.132.052.05 S15 ppm-12.989 10ppm 910 89 78 67 56 45 34 23 12 0

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 170.122 135.638 134.199 130.516 129.068 126.012 125.836 67.016 66.968 47.280 41.931 19.033 4d S16 0 ppm-238.897 200ppm 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 8.321 8.299 7.616 7.594 3.823 3.409 2 4e 1.87 1.87 2 2 8.32 8.32 S17 ppm-12.989 10ppm 910 89 78 67 56 45 34 23 12 01

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 168.073 148.517 141.434 128.168 123.991 66.762 48.043 42.596 2 4e S18 0 ppm-238.897 200ppm 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 7.434 7.412 7.399 7.121 7.100 7.078 3.707 3.366 1.702 1.569 F 4f 2 2 1.821.82 2.17 2.17 2.1 2.1 1.911.91 4.094.09 S19 ppm-12.989 10ppm 910 89 78 67 56 45 34 23 12 01

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 169.405 164.448 161.975 132.487 132.454 129.118 129.033 115.550 115.332 48.904 43.227 26.555 25.736 24.565 F 4f S20 0 ppm-238.897 200ppm 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 7.409 7.345 3.712 3.351 1.701 1.541 Cl 4g 4 4 2.16 2.16 2.232.23 4.254.25 2.29 2.29 S21 ppm-12.989 10ppm 910 89 78 67 56 45 34 23 12 01

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 169.229 135.408 134.826 128.674 128.360 48.858 43.256 26.554 25.628 24.542 Cl 4g S22 0 ppm-238.897 200ppm 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 7.568 7.547 7.302 7.285 3.711 1.700 1.540 Br 4h 1.99 1.99 2.16 2.16 2.32 2.32 1.671.67 2 2 4.4 4.4 S23 ppm-12.989 10ppm 910 89 78 67 56 45 34 23 12 01

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 169.259 135.276 131.639 128.563 123.634 48.797 43.344 26.543 25.612 24.528 Br 4h S24 0 ppm-238.897 200ppm 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 7.404 7.272 3.720 3.348 1.734 1.553 Cl 4i 3.97 3.97 2 2 2.192.19 4.284.28 1.83 1.83 S25 ppm-12.989 10ppm 910 89 78 67 56 45 34 23 12 01

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 168.707 138.240 134.509 129.827 129.521 127.027 124.892 76.716 48.777 43.201 26.586 25.578 24.541 Cl 4i S26 0 ppm-238.897 200ppm 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 7.472 7.202 4.789 4.538 3.056 2.887 4j 0.978 0.978 3.06 3.06 9.86 9.86 1 1 S27 ppm-12.989 10ppm 910 89 78 67 56 45 34 23 12 01

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 171.606 170.761 137.068 136.604 136.263 129.609 128.752 128.445 128.185 127.914 127.557 126.997 126.812 55.197 50.803 37.009 33.201 4j S28 0 ppm-238.897 200ppm 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 7.481 7.478 7.468 7.466 7.422 7.296 6.996 6.987 6.984 6.974 4.754 S 4k 11.4 11.4 4.15 4.15 0.9720.972 0.971 0.971 S29 ppm-12.989 10ppm 910 89 78 67 56 45 34 23 12 01

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 165.069 137.668 136.574 129.343 128.828 128.607 127.598 126.899 50.121 S 4k S30 0 200ppm-218.761 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 7.215 3.793 3.710 3.174 2.307 1.662 1.461 4l 2.09 2.09 3 3 2.1 2.1 4.16 4.16 2.03 2.03 4.09 4.09 S31 ppm-14.668 10ppm 910 89 78 67 56 45 34 23 12 0

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 169.793 136.724 133.967 130.246 128.499 125.760 125.561 47.807 42.330 26.525 25.683 24.519 18.918 4l S32 0 200ppm-218.761 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry S 4m H 0.823 0.991 0.823 1.3 1.3 1.16 1.16 1.131.13 3.96 13.96 1 1.141.14 S33 ppm 10ppm 910 89 78 67 56 45 34 23 12 01

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 161.758 138.733 138.019 130.004 128.789 128.142 127.943 127.673 127.628 44.021 S 4m H S34 0 ppm-238.897 200ppm 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 6.189 3.495 3.477 3.462 3.444 1.658 1.622 1.409 1.382 1.364 0.953 0.936 0.918 H 4n 3 1.89 1.89 3 1.141.14 2.382.38 4.344.34 2.97 2.372.37 2.97 S35 ppm-12.989 10ppm 910 89 78 67 56 45 34 23 12 01

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 167.500 134.884 131.282 128.527 126.808 40.085 29.377 29.150 22.394 13.993 H 4n S36 0 ppm-238.897 200ppm 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 7.868 7.847 7.686 7.624 7.504 7.466 7.426 7.390 6.181 3.525 3.507 3.492 3.474 1.679 1.633 1.419 1.320 0.932 0.915 0.898 H 4o 4.14 4.140.879 2 2 2.02 2.02 1.021.02 2.292.29 8.328.32 3.07 2.242.24 3.07 S37 ppm-12.989 10ppm 910 89 78 67 56 45 34 23 12 01

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 167.173 144.128 140.060 133.528 128.898 127.944 127.338 127.214 127.189 40.152 31.762 29.732 29.011 26.992 22.603 14.072 H 4o S38 0 ppm-238.897 200ppm 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 8.325 8.304 7.937 7.880 7.612 7.525 7.488 7.450 6.004 3.595 3.544 1.709 1.636 1.529 1.436 1.031 0.994 H 4p 1.74 0.785 0.785 1.74 0.991 0.991 2.82 2.82 0.81 0.81 2 2 2.162.16 2.86 2.352.35 2.86 S39 ppm-12.989 10ppm 910 89 78 67 56 45 34 23 12 01

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 169.559 134.913 133.675 130.413 130.123 128.278 127.055 126.391 125.406 124.721 39.807 31.796 20.190 13.803 H 4p S40 0 ppm-238.897 200ppm 180200 160180 140160 120140 100120 80100 6080 4060 2040 020

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 8.100 8.079 7.769 7.748 7.377 7.253 6.218 3.955 3.783 3.766 3.751 3.734 2.990 2.973 2.956 H 4q 1.99 1.921.92 1.99 4.884.88 1.071.07 2.342.34 3.133.13 2.31 2.31 S41 ppm-12.989 10ppm 910 89 78 67 56 45 34 23 12 01

Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry 166.590 166.270 138.697 138.536 132.658 129.839 128.796 128.774 126.864 126.704 52.382 41.243 35.602 H 4q 1 1 S42 ppm-238.897 200ppm 180200 160180 140160 120140 100120 80100 6080 4060 2040 020