Three-component synthesis of α-branched amines under Barbier-like conditions

Transcription

1 Three-component synthesis of α-branched amines under Barbier-like conditions Erwan Le Gall*, Caroline Haurena, Stéphane Sengmany, Thierry Martens and Michel Troupel Électrochimie et Synthèse Organique, Institut de Chimie et des Matériaux Paris Est (ICMPE), UMR 7182 CNRS - Université Paris 12, 2-8 rue Henri-Dunant, F Thiais, France *legall@glvt-cnrs.fr SUPPORTING INFORMATION Table of Contents General:...S2 Typical experimental procedures:...s2 Characterization data:...s4 Supporting references:...s13 NMR spectra:...s14 Chromatograms:...S89 S1

2 General: Solvents and reagents were purchased from commercial suppliers and used without further purification. All reactions were monitored by gas chromatography (GC). Melting points (mp) are uncorrected. Infrared spectra were recorded on a FT-IR spectrometer in ATR mode. NMR spectra were recorded in CDCl 3 at 400 MHz ( 1 H), 100 MHz ( 13 C) and 376 MHz ( 19 F). Chemical shifts (δ) are reported in parts per million (ppm) relative to the residual non-deuterated solvent signal. Coupling constant values (J) are given in Hertz (Hz) and refer to apparent multiplicities, indicated as follows: s (singlet); br s (broad singlet); d (doublet); t (triplet); q (quartet); m (multiplet); dd (doublet of doublets). Mass spectra were measured on a GC/MS apparatus. Elemental analyses were performed by an outside facility. For compounds that did not return a satisfactory elemental analysis (compounds 1f, 1k, 1l, 1o, 2i, 2j, 4a and 4d), a copy of a chromatogram obtained using gas chromatography is furnished. Compounds which have been previously described in the literature are linked to the corresponding bibliographic references whereas compounds labeled by asterisk (*) are, to the best of our knowledge, new compounds. Typical procedure for the coupling of benzyl bromide, 2-(bromomethyl)naphtalene or ethyl bromoacetate with an amine and an aldehyde (Preparation of compounds 1a-o, 4a and 4b): A dried 100 ml round-bottom flask was flushed with argon and charged with acetonitrile (40 ml). Zinc dust (2.0 g, 30 mmol), benzyl bromide (0.4 ml) and trifluoroacetic acid (0.2 ml) were added and the resulting solution stirred for additional 5 minutes. Then the organic bromide (25 mmol), the amine (10 mmol) and the aldehyde (11 mmol) were introduced to the mixture, and the solution stirred at room temperature for 1 h (exothermic reaction). The resulting solution was poured to a saturated aqueous NH 4 Cl solution (150 ml), then extracted with CH 2 Cl 2 (2 100 ml). The combined organic layers were dried over Na 2 SO 4 and evaporated to dryness. The crude product was purified over neutral alumina (Merck, aluminium oxide 90 active neutral) using a solvent gradient (pentane/dichloromethane 70:30 0:100). Alternatively, the pure product could be obtained from the crude oil using an acid-base work-up, 1 as detailed below. Typical procedure for the coupling of a functionalized benzyl bromide with an amine and benzaldehyde (Preparation of compounds 2a-j): A dried 100 ml round-bottom flask was flushed with argon and charged with acetonitrile (20 ml). Zinc dust (1.0 g, 15 mmol), benzyl bromide (0.2 ml) and trifluoroacetic acid (0.1 ml) were added and the resulting solution stirred for additional 5 minutes. Then the functionalized benzyl bromide (12.5 mmol), the amine (5 mmol) and benzaldehyde (0.55 ml, 5.5 mmol) were introduced to the mixture, and the solution stirred at room temperature for 1 h (exothermic reaction). The resulting solution was poured to a saturated aqueous NH 4 Cl solution (100 ml), then extracted with CH 2 Cl 2 (2 50 ml). The combined organic layers were dried over Na 2 SO 4 and evaporated to dryness. The crude product was purified over neutral alumina (Merck, aluminium oxide 90 active neutral) column using a solvent gradient (pentane/diethyl ether 100:0 50:50). Alternatively, the pure product could be obtained from the crude oil using an acid-base work-up, as detailed below. S2

3 Procedure for the coupling of allyl chloride with aniline and benzaldehyde (Preparation of compound 4c): A dried 100 ml round-bottom flask was flushed with argon and charged with acetonitrile (40 ml) and DMF (5 ml). Bu 4 NI (3.69 g, 10 mmol), zinc dust (2.7 g, 40 mmol), allyl chloride (0.4 ml) and trifluoroacetic acid (0.2 ml) were added and the resulting solution stirred for additional 5 minutes. Then allyl chloride (2 ml, 25 mmol), aniline (0.91 ml, 10 mmol) and benzaldehyde (1.1 ml, 11 mmol) were introduced to the mixture which was stirred at 60 C for 18 h. The resulting solution was poured to a saturated aqueous NH 4 Cl solution (150 ml), then extracted with CH 2 Cl 2 (2 100 ml). The combined organic layers were dried over Na 2 SO 4 and evaporated to dryness. The crude product was purified over silica gel (SDS µm) using a 95:5 pentane/diethyl ether mixture as eluant. Typical procedure for the coupling of an aryl bromide or a vinylic bromide with an amine and an aldehyde (Preparation of compounds 3a-f and 4d): A dried 100 ml round-bottom flask was flushed with argon and charged with acetonitrile (40 ml). Cobalt bromide (0.66 g, 3 mmol), zinc bromide (0.68 g, 3 mmol), zinc dust (6 g, 92 mmol), phenyl bromide (0.32 ml, 3 mmol) and trifluoroacetic acid (0.2 ml) were added and the resulting solution stirred for additional 5 minutes. Then the aryl bromide (30 mmol), the amine (10 mmol) and the aldehyde (10 mmol) were introduced to the mixture which was stirred at 60 C for 2 h. The resulting solution was poured to a saturated aqueous NH 4 Cl solution (150 ml), then extracted with CH 2 Cl 2 (2 100 ml). The combined organic layers were dried over Na 2 SO 4 and evaporated to dryness. The crude product was purified over silica gel (SDS µm) using a 80:20 pentane/diethyl ether mixture as eluant. Alternatively, the pure product could be obtained from the crude oil using an acid-base work-up, as detailed below. Typical acid-base work-up (10 mmol scale): The crude oil was dissolved in diethyl ether (150 ml). Concentrated sulphuric acid ( ml) was added carefully to the vigorously-stirred solution and allowed to react for 5 min. The resulting ammonium salt was filtered and washed with diethyl ether (2 50 ml). The solid was then poured, under stirring, into a 5% aqueous NaOH solution (100 ml) and extracted with CH 2 Cl 2 (2 100 ml). The combined organic fractions were dried over Na 2 SO 4 and concentrated to dryness yielding the analytically-pure product (> 97% GC). S3

4 (1,2-Diphenylethyl)piperidine (1a) 2 : Pale yellow oil. m = 2.05 g (77%). ATR-FTIR (neat, cm -1 ): 3026, 2930, 1495, 1451, 748, H NMR (400 MHz): δ (m, 8H), 7.07 (d, J = 7.0 Hz, 2H), 3.66 (dd, J = 9.4 Hz, J = 5.2 Hz, 1H), 3.39 (dd, J = 13.3 Hz, J = 5.2 Hz, 1H), 3.66 (dd, J = 13.3 Hz, J = 9.5 Hz, 1H), (m, 4H), (m, 4H), (m, 2H). 13 C NMR (100 MHz): δ 139.9, 139.3, 129.4, 129.0, 127.9, 127.7, 126.9, 125.7, 72.4, 51.4, 39.2, 26.4, MS, m/z (%): 175 (14), 174 ([M- CH 2 Ph] +, 100), 91 (21). Anal. Calcd for C 19 H 23 N: C, 85.99; H, 8.74; N, Found: C, 86.32; H, 8.93; N, (1,2-Diphenylethyl)indoline (1b)*: Brown oil. m = 2.2 g (74%). ATR-FTIR (neat, cm -1 ): 3060, 3026, 2925, 2846, 1604, 1472, 1453, 1252, 739, H NMR (400 MHz): δ (m, 10H), (m, 2H), 6.66 (t, J = 7.3 Hz, 1H), 6.54 (d, J = 7.8 Hz, 1H), 4.99 (t, J = 7.5 Hz, 1H), 3.67 (q, J = 8.5 Hz, 1H), (m, 3H), (m, 2H). 13 C NMR (100 MHz): δ 151.2, 140.2, 139.2, 129.9, 129.1, 128.4, 128.1, 127.3, 126.2, 124.5, 116.8, 106.8, 60.9, 47.9, 37.5, MS, m/z (%): 209 (16), 208 ([M- CH 2 Ph] +, 100), 193 (5), 165 (5), 130 (8), 115 (5), 91 (19). Anal. Calcd for C 22 H 21 N: C, 88.25; H, 7.07; N, Found: C, 88.15; H, 7.24; N, N-benzyl-(1,2-diphenylethyl)amine (1c) 3 : Pale yellow solid. m = 2.19 g (76%). mp C. ATR-FTIR (neat, cm -1 ): 3304, H N 7.46; N, , 1492, 1453, 1228, 1152, 729, H NMR (400 MHz): δ (m, 11H), 7.21 (d, J = 7.3 Hz, 4H), (m, 1H), 3.76 (AB, J = 13.5 Hz, 1H), 3.57 (AB, J = 13.5 Hz, 1H), (m, 2H), 1.85 (br s, 1H). 13 C NMR (100 MHz): δ 143.8, 140.4, 138.9, 129.4, (2 peaks), 128.4, 128.0, 127.5, 127.2, 126.8, 126.4, 63.7, 51.4, MS, m/z (%): 197 (11), 196 (80), 92 (8), 91 (100), 65 (8). Anal. Calcd for C 21 H 21 N: C, 87.76; H, 7.36; N, Found: C, 87.41; H, 1,2-Diphenyl-N-[(R)-1-phenylethyl]ethylamine (1d) 4, major diastereoisomer: Pale yellow oil. m = 1.67 g (58%). ATR-FTIR (neat, cm -1 ): 3321, 3062, 3026, H N Me 2963, 2922, 1601, 1493, 1452, 758, H NMR (400 MHz): δ (m, 13H), 7.07 (d, J = 7.1 Hz, 2H), 4.01 (t, J = 6.8 Hz, 1H), 3.76 (q, J = 6.5 Hz, 1H), (m, 2H), 1.67 (br s, 1H), 1.32 (d, J = 6.5 Hz, 3H). 13 C NMR (100 MHz): δ 146.0, 143.8, 138.9, 129.4, 128.4, 128.3, 128.2, 127.4, 127.0, 126.8, 126.6, 126.2, 61.9, 54.7, 44.5, MS, m/z (%): 211 (10), 210 (59), 166 (5), 165 (7), 107 (8), 106 (100), 105 (50), 103 (9), 79 (17), 77 (9). Anal. Calcd for C 22 H 23 N: C, 87.66; H, 7.69; N, Found: C, 87.45; H, 7.87; N, S4

5 N-(1,2-diphenylethyl)n-propylamine (1e) 5 : Pale yellow oil. m = 2.06 g (86%). ATR-FTIR (neat, cm -1 ): 3322, 3026, 2957, 2929, 1602, 1494, 1453, 756, H NMR (400 MHz): δ (m, 10H), (m, 1H), (m, 2H), (m, 2H), (m, 3H), 0.83 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz): δ 144.0, 139.0, 129.3, 128.4, 128.3, 127.3, 127.0, 126.3, 64.8, 49.7, 45.4, 23.1, MS, m/z (%): 240 ([M+1] +, 6), 149 (11), 148 ([M-CH 2 Ph] +, 100), 106 (27), 79 (13). Anal. Calcd for C 17 H 21 N: C, 85.30; H, 8.84; N, Found: C, 84.92; H, 8.95; N, N-(1,2-diphenylethyl)prop-2-en-1-amine (1f) 6 : Orange oil. m = 1.74 g (73%). ATR-FTIR (neat, cm -1 ): 3325, 3027, 2918, 1642, 1602, 1494, 1453, 915, 757, H NMR (400 MHz): δ (m, 8H), 7.19 (d, J = 7.3 Hz, 2H), (m, 1H), 5.08 (d, J = 4.9 Hz, 1H), 5.05 (s, 1H), (m, 1H), (m, 1H), (m, 3H), 1.39 (s, 1H). 13 C NMR (100 MHz): δ 143.6, 138.7, 136.8, 129.3, (2 peaks), 127.4, 127.1, 126.4, 115.6, 63.9, 50.0, MS, m/z (%): 165 (5), 147 (12), 146 ([M-CH 2 Ph] +, 100), 129 (7), 104 (5), 92 (5), 91 (36). Anal. Calcd for C 17 H 19 N: C, 86.03; H, 8.07; N, Found: C, 85.17; H, 8.16; N, N-(1,2-diphenylethyl)aniline (1g) 3 : Pale brown solid. m = 2.43 g (89%). mp C. ATR-FTIR (neat, cm -1 ): 3410, 3025, 2932, 2907, 1599, 1504, 748, H NMR (CDCl 3, 400 MHz): δ (m, 8H), 7.19 (d, J = 7.2 Hz, 2H), 7.12 (t, J = 7.7 Hz, 2H), 6.70 (t, J = 7.3 Hz, 1H), 6.53 (d, J = 8.0 Hz, 2H), (m, 1H), 4.23 (br s, 1H), (m, 2H). 13 C NMR (100 MHz): δ 147.3, 143.4, 137.7, 129.3, 129.1, (2 peaks), 127.1, 126.8, 126.5, 117.6, 113.7, 59.3, MS, m/z (%): 183 (15), 182 ([M-CH 2 Ph] +, 100), 180 (6), 104 (25), 77 (14). Anal. Calcd for C 20 H 19 N: C, 87.87; H, 7.01; N, Found: C, 87.69; H, 7.22; N, N-(1,2-diphenylethyl)-3,5-dimethoxyaniline (1h)*: Pale brown solid. m = 2.80 g (84%). mp C. ATR-FTIR (neat, cm -1 ): 3404, 3019, 2961, 2934, 1615, 1200, 1144, 807, H NMR (400 MHz): δ (m, 8H), 7.16 (d, J = 7.1 Hz, 2H), 5.86 (s, 1H), 5.72 (s, 2H), 4.63 (t, J = 6.9 Hz, 1H), 4.20 (br s, 1H), 3.68 (s, 6H), (m, 2H). 13 C NMR (100 MHz): δ 161.5, 149.2, 143.3, 137.6, 129.2, 128.6, 127.1, 126.7, 126.4, 92.6, 90.0, 59.3, 55.0, MS, m/z (%): 243 (16), 242 ([M-CH 2 Ph] +, 100), 226 (7), 137 (10). Anal. Calcd for C 22 H 23 NO 2 : C, 79.25; H, 6.95; N, Found: C, 78.93; H, 7.07; N, S5

6 N-[2-phenyl-1-[2-(trifluoromethyl)phenyl]ethyl]n-propylamine (1i)*: Pale yellow oil. m = 1.67 g (54%). ATR-FTIR (neat, cm -1 ): 3326, 3029, 2960, 2928, 1606, 1454, 1309, 1156, 1034, 768, 698, H NMR (400 MHz): δ 7.86 (d, J = 7.9 Hz, 1H), 7.55 (d, J = 7.9 Hz, 1H), 7.49 (t, J = 7.5 Hz, 1H), (m, 6H), 4.26 (d, J = 9.7 Hz, 1H), 2.94 (dd, J = 13.5 Hz, J = 2.3 Hz, 1H), 2.55 (dd, J = 13.4 Hz, J = 10.2 Hz, 1H), (m, 2H), (m, 3H), 0.61 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz): δ 144.3, 138.8, 132.1, 129.2, 128.6, 128.4, (q, J = 29.6 Hz), 126.7, 126.6, (q, J = 6.0 Hz), (q, J = Hz), 59.2, 49.5, 45.3, 22.9, F NMR (376 MHz): δ MS, m/z (%): 217 (7), 216 (60), 209 (9), 196 (6), 155 (9), 154 (100), 134 (23). Anal. Calcd for C 18 H 20 F 3 N: C, 70.44; H, 6.56; N, Found: C, 70.76; H, 6.74; N, N-[1-[4-(methylthio)phenyl]-2-phenylethyl]n-propylamine (1j)*: Yellow oil. m = 2.0 g (70%). ATR-FTIR (neat, cm -1 ): 3322, 3026, 2957, 2871, 1697, 1620, 1493, 1091, 815, 747, H NMR (CDCl 3, 400 MHz): δ (m, 7H), 7.18 (d, J = 7.5 Hz, 2H), 3.86 (t, J = 7.0 Hz, 1H), (m, 2H), 2.51 (s, 3H), (m, 2H), (m, 3H), 0.82 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz): δ 141.2, 138.9, 136.5, 129.3, 128.4, 127.9, 126.7, 126.4, 64.4, 49.7, 45.3, 23.1, 16.0, MS, m/z (%): 196 (5), 195 (15), 194 ([M-CH 2 Ph] +, 100), 179 (9), 178 (5), 152 (35), 137 (6), 125 (16), 109 (9). Anal. Calcd for C 18 H 23 NS: C, 75.74; H, 8.12; N, Found: C, 75.76; H, 8.28; N, N-[1-(4-fluorophenyl)-2-phenylethyl]prop-2-en-1-amine (1k)*: Pale yellow solid. m = 1.72 g (67%). mp C. ATR-FTIR (neat, cm -1 ): H N 3327, 3028, 2918, 1602, 1508, 1454, 1220, 1155, 833, H NMR (400 F MHz): δ (m, 5H), 7.14 (d, J = 7.3 Hz, 2H), 7.03 (t, J = 8.5 Hz, 2H), (m, 1H), (m, 2H), 3.94 (t, J = 7.0 Hz, 1H), (m, 4H), 1.61 (br s, 1H). 13 C NMR (100 MHz): δ (d, J = Hz), (d, J = 3.0 Hz), 138.5, 136.7, 129.3, (d, J = 7.9 Hz), 128.4, 126.5, 115.7, (d, J = 21.2 Hz), 63.2, 49.9, F NMR (376 MHz): δ MS, m/z (%): 165 (11), 164 ([M-CH 2 Ph] +, 100), 122 (6), 109 (21). Anal. Calcd for C 17 H 18 FN: C, 79.97; H, 7.11; N, Found: C, 79.13; H, 7.06; N, N-[2-phenyl-1-(thiophen-3-yl)ethyl]prop-2-en-1-amine (1l)*: Brown oil. m = 2.03 g (83%). ATR-FTIR (neat, cm -1 ): 3027, 2977, 2929, 1494, 1453, 917, 781, H NMR (400 MHz): δ (m, 4H), (m, 4H), (m, 1H), (m, 2H), 4.08 (t, J = 6.9 Hz, 1H), (m, 4H), 1.59 (br s, 1H). 13 C NMR (100 MHz): δ 144.9, 138.7, 136.8, 129.3, 128.4, (2 peaks), 125.6, 121.4, 115.8, 59.4, 50.0, MS, m/z (%): 154 (7), 153 (13), 152 ([M-CH 2 Ph] +, 100), 135 (7), 125 (6), 97 (36), 91 (8). Anal. Calcd for C 15 H 17 NS: C, 74.03; H, 7.04; N, Found: C, 72.47; H, 7.12; N, S6

7 N-(1-phenyloctan-2-yl)aniline (1m) 3 : Pale brown oil. m = 2.21 g (79%). ATR-FTIR (neat, cm -1 ): 3405, 3025, 2926, 1600, 1504, 1318, 745, H NMR (400 MHz): δ (m, 7H), 6.58 (t, J = 7.3 Hz, 1H), 6.51 (d, J = 7.8 Hz, 2H), (m, 1H), 3.32 (br s, 1H), m, 2H), (m, 10H), 0.77 (t, J = 6.6 Hz, 3H). 13 C NMR (100 MHz): δ 147.7, 138.7, 129.7, 129.5, 128.3, 126.2, 117.0, 113.3, 53.7, 40.2, 34.1, 31.9, 29.5, 26.2, 22.7, MS, m/z (%): 191 (13), 190 ([M-CH 2 Ph] +, 100), 118 (9), 106 (39), 91 (6), 55 (6). Anal. Calcd for C 20 H 27 N: C, 85.35; H, 9.67; N, Found: C, 85.68; H, 9.75; N, Ethyl 2-morpholino-3-phenylpropanoate (1n) 7 : Pale yellow oil. m = 2.19 g (83%). ATR-FTIR (neat, cm -1 ): 2959, 1725, 1453, O 1154, 1115, H NMR (400 MHz): δ (m, 5H), (m, 2H), N (m, 4H), 3.42 (dd, J = 9.3 Hz, J = 6.0 Hz, 1H), (m, 2H), (m, 4H), 1.16 (t, J = 7.1 Hz, 3H). 13 C NMR (100 MHz): δ 170.9, 137.8, CO 2 Et 129.2, 128.2, 126.5, 69.8, 67.3, 60.2, 50.2, 35.4, MS, m/z (%): 191 (9), 190 (79), 173 (8), 172 ([M-CH 2 Ph] +, 100), 144 (36), 105 (10), 91 (6). Anal. Calcd for C 15 H 21 NO 3 : C, 68.42; H, 8.04; N, Found: C, 68.12; H, 8.15; N, Phenethylpiperidine (1o) 8 : Pale yellow oil. m = 1.71 g (90%). ATR-FTIR (neat, cm -1 ): 3026, 2932, 1602, 1452, 1154, 1113, 744, H NMR (400 MHz): δ (m, 5H), (m, 2H), (m, 2H), 2.49 (br s, 4H), 1,65 (dt, J = 11.2 Hz, J = 5.6 Hz, 4H), (m, 2H). 13 C NMR (100 MHz): δ 140.7, 128.7, 128.4, 126.0, 61.5, 54.6, 33.7, 26.1, MS, m/z (%): 105 (5), 99 (8), 98 ([M-CH 2 Ph] +, 100), 96 (6), 70 (28). Anal. Calcd for C 13 H 19 N: C, 82.48; H, 10.12; N, Found: C, 81.48; H, 10.14; N, [2-(4-Bromophenyl)-1-phenylethyl]piperidine (2a)*: Pale orange oil. m = 1.04 g (59%). ATR-FTIR (neat, cm -1 ): 3025, 2931, 1486, 1451, 1070, 1011, 804, H NMR (400 MHz): δ (m, 5H), 7.12 (d, J = 6.5 Hz, 2H), 6.88 (d, J = 8.4 Hz, 2H), 3.55 (dd, J = 9.3 Hz, J = 5.4 Hz, 1H), 3.27 (dd, J = 13.4 Hz, J = 5.4 Hz, 1H), 2.96 (dd, 13.4 Hz, J = 9.3 Hz, 1H), (m, 4H), (m, 4H), (m, 2H). 13 C NMR (100 MHz): δ 138.9, 131.1, 130.9, 128.9, 127.8, 127.0, 119.5, 72.1, 51.4, 38.6, 26.3, MS, m/z (%): 175 (14), 174 ([M-BrPhCH 2 ] +, 100), 91 (18). Anal. Calcd for C 19 H 22 BrN: C, 66.28; H, 6.44; N, Found: C, 66.62; H, 6.50; N, S7

8 1-[2-(3-fluorophenyl)-1-phenylethyl)piperidine (2b)*: Pale yellow solid. m = 0.50 g (35%). mp: C. ATR-FTIR (neat, cm -1 ): 3028, F 2932, 1614, 1588, 1488, 1448, 1248, 1139, H NMR (400 MHz): δ (m, 6H), (m, 3H), 3.50 (dd, J = 9.1 Hz, J = 5.4 Hz, 1H), 3.22 (dd, J = 13.3 Hz, J = 5.3 Hz, 1H), 2.89 (dd, 12.9 Hz, J = 9.7 Hz, 1H), (m, 4H), (m, 4H), (m, 2H). 13 C NMR (100 MHz): δ (d, J = Hz), (d, J = 7.4 Hz), 138.8, (d, J = 8.3 Hz), 128.9, 127.8, (d, J = 2.7 Hz), (d, J = 21.0 Hz), (d, J = 21.0 Hz), 72.1, 51.4, 38.8, 26.2, F NMR (376 MHz): δ MS, m/z (%): 175 (12), 174 ([M-FPhCH 2 ] +, 100), 91 (23). Anal. Calcd for C 19 H 22 FN: C, 80.53; H, 7.82; N, Found: C, 80.85; H, 7.97; N, [2-phenyl-2-(piperidin-1-yl)ethyl]benzonitrile (2c)*: Yellow oil. m = 1.03 g (71%). ATR-FTIR (neat, cm -1 ): 3027, 2932, 2223, 1600, CN N N 1487, 1450, 1095, 756, H NMR (400 MHz): δ 7.51 (d, J = 7.7 Hz, 1H), (m, 7H), 7.04 (d, J = 7.8 Hz, 1H), (m, 2H), 3.12 (dd, J = 8.5 Hz, J = 13.1 Hz, 1H), (m, 4H), (m, 4H), (m, 2H). 13 C NMR (100 MHz): δ 144.0, 139.0, 132.5, 132.1, 130.7, 128.7, 127.9, 127.2, 118.4, 112.9, 71.4, 51.6, 37.6, 26.3, MS, m/z (%): 175 (15), 174 ([M- NCPhCH 2 ] +, 100), 91 (17). Anal. Calcd for C 20 H 22 N 2 : C, 82.72; H, 7.64; N, Found: C, 82.40; H, 7.46; N, [2-phenyl-2-(propylamino)ethyl]benzonitrile (2d)*: Pale yellow solid. m = 0.61 g (46%). mp C. ATR-FTIR (neat, cm -1 ): 3029, 2957, 2924, 2224, 1604, 1453, 759, H NMR (400 MHz): δ 7.50 (d, J = 8.0 Hz, 2H), (m, 7H), 3.85 (t, J = 7.0 Hz, 1H), (m, 2H), 2.40 (t, J = 7.2 Hz, 2H), (m, 3H), 0.82 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz): δ 144.7, 142.9, 132.0, 130.2, 128.4, 127.3, 127.2, 119.0, 110.1, 64.5, 49.6, 45.1, 23.2, MS, m/z (%): 149 (11), 148 ([M-NCPhCH 2 ] +, 100), 106 (28), 79 (11). Anal. Calcd for C 18 H 20 N 2 : C, 81.78; H, 7.63; N, Found: C, 81.54; H, 7.58; N, N-[2-(4-bromophenyl)-1-phenylethyl]prop-2-en-1-amine (2e)*: Pale orange oil. m = 1.03 g (65%). ATR-FTIR (neat, cm -1 ): 3324, 3062, 3025, 2919, 2833, 1642, 1487, 1453, 1071, 1011, 915, 803, 756, H NMR (400 MHz): δ (m, 7H), 6.99 (d, J = 7.9 Hz, 2H), (m, 1H), (m, 2H), 3.90 (t, J = 7.0 Hz, 1H), 3.14 (dd, J = 14.2 Hz, J = 4.7 Hz, 1H), 3.01 (dd, J = 14.2 Hz, J = 6.5 Hz, 1H), 2.92 (d, J = 6.8 Hz, 2H), 1.50 (br s, 1H). 13 C NMR (100 MHz): δ 143.1, 137.7, 136.7, 131.4, 131.1, 128.4, (2 peaks), 120.2, 115.8, 63.7, 50.0, MS, m/z (%): 179 (5), 178 (6), 165 (5), 147 (11), 146 ([M-BrPhCH 2 ] +, 100), 129 (8), 104 (7), 91 (35), 90 (8), 89 (5). Anal. Calcd for C 17 H 18 BrN: C, 64.57; H, 5.74; N, Found: C, 64.30; H, 5.75; N, S8

9 N-[2-[4-(methylthio)phenyl]-1-phenylethyl]aniline (2f)*: Pale brown oil. m = 0.88 g (55%). ATR-FTIR (neat, cm -1 ): 3399, 3021, 2920, 1600, 1504, 1493, 748, H NMR (400 MHz): δ (m, 5H), 7.33 (d, J = 8.3 Hz, 2H), (m, 4H), 6.82 (t, J = 7.3 Hz, 1H), 6.66 (d, J = 8.6 Hz, 2H), 4.75 (dd, J = 7.8 Hz, J = 6.0 Hz, 1H), 4.31 (br s, 1H), (m, 2H), 2.57 (s, 3H). 13 C NMR (100 MHz): δ 147.4, 143.4, 136.8, 134.7, 129.9, 129.3, 128.8, 127.3, 126.9, 126.7, 117.9, 113.9, 59.3, 44.6, MS, m/z (%): 183 (15), 182 ([M-MeSPhCH 2 ] +, 100), 104 (22), 77 (10). Anal. Calcd for C 21 H 21 NS: C, 78.95; H, 6.63; N, Found: C, 79.19; H, 6.76; N, [2-phenyl-2-(phenylamino)ethyl]benzonitrile (2g)*: Pale brown solid. m = 1.44 g (96%). mp: C. ATR-FTIR (neat, cm -1 ): 3397, 3064, 3022, 2951, 2226, 1600, 1515, 1497, 1450, 1306, 748, H NMR (400 MHz): δ 7.66 (d, J = 6.8 Hz, 1H), (m, 8H), 7.13 (dd, J = 8.4 Hz, J = 7.4 Hz, 2H), 6.71 (t, J = 7.3 Hz, 1H), 6.60 (d, J = 7.7 Hz, 2H), 4.80 (dd, J = 8.4 Hz, J = 6.0 Hz, 1H), 4.36 (br s, 1H), (m, 2H). 13 C NMR (100 MHz): δ 146.7, 142.4, 142.3, 133.0, 132.9, 130.5, 129.2, 128.9, 127.6, 127.4, 126.5, 118.5, 117.9, 113.8, 113.0, 59.1, MS, m/z (%): 183 (14), 182 ([M-NCPhCH 2 ] +, 100), 104 (25), 77 (13). Anal. Calcd for C 21 H 18 N 2 : C, 84.53; H, 6.08; N, Found: C, 84.36; H, 6.01; N, N-[1-phenyl-2-[3-(trifluoromethyl)phenyl]ethyl]aniline (2h)*: Pale brown solid. m = 1.23 g (72%). mp: C. ATR-FTIR (neat, cm -1 ): 3400, 3030, 2922, 1599, 1508, 1319, 1153, 1117, 1071, 804, H NMR (400 MHz): δ 7.54 (d, J = 7.8 Hz, 1H), (m, 8H), 7.14 (t, J = 7.9 Hz, 2H), 6.71 (t, J = 7.0 Hz, 1H), 6.57 (d, J = 7.7 Hz, 2H), 4.67 (t, J = 6.9 Hz, 1H), 4.17 (br s, 1H), 3.20 (d, J = 7.1 Hz, 2H). 13 C NMR (100 MHz): δ 146.9, 142.6, 138.7, 132.6, (q, J = 32.1 Hz), 129.2, 128.9, 128.7, 127.4, 126.5, (q, J = 3.7 Hz), (q, J = Hz), (q, J = 3.8 Hz), 117.8, 113.7, 59.2, F NMR (376 MHz): δ MS, m/z (%): 183 (14), 182 ([M-F 3 CPhCH 2 ] +, 100), 104 (23), 77 (10). Anal. Calcd for C 21 H 18 F 3 N: C, 73.89; H, 5.31; N, Found: C, 73.78; H, 5.34; N, Methyl 4-[2-phenyl-2-(phenylamino)ethyl]benzoate (2i)*: Brown oil. m = 1.35 g (81%). ATR-FTIR (neat, cm -1 ): 3402, 3023, 2956, 1699, 1598, 1509, 1446, 1431, 1278, 1205, 1109, 747, 701, H NMR (400 MHz): δ (m, 2H), (m, 7H), 7.17 (t, J = 7.0 Hz, 2H), 6.75 (t, J = 7.3 Hz, 1H), 6.61 (d, J = 8.5 Hz, 2H), 4.73 (dd, J = 7.9 Hz, J = 6.2 Hz, 1H), 4.32 (br s, 1H), 3.99 (s, 3H), (m, 2H). 13 C NMR (100 MHz): δ 167.2, 147.2, 143.2, 138.5, 133.9, 130.5, 130.4, 129.2, 128.8, 128.7, 128.1, 127.3, 126.6, 117.7, 113.8, 59.4, 52.2, MS, m/z (%): 300 (5), 183 (15), 182 ([M-MeO 2 CPhCH 2 ] +, 100), 104 (15), 77 (8). Anal. Calcd for C 22 H 21 NO 2 : C, 79.73; H, 6.39; N, Found: C, 78.95; H, 6.39; N, S9

10 N-[2-[4-(methylsulfonyl)phenyl]-1-phenylethyl]aniline (2j)*: Pale brown solid. m = 1.06 g (60%). mp C (dec.). ATR-FTIR (neat, cm -1 ): 3408, 3052, 1602, 1504, 1296, 1144, H NMR (400 MHz): δ 7.73 (d, J = 8.3 Hz, 2H), (m, 7H), (m, 2H), 6.63 (t, J = 7.3 Hz, 1H), 6.50 (d, J = 8.0 Hz, 2H), 4.55 (t, J = 7.0 Hz, 1H), (m, 2H), 2.94 (s, 3H). 13 C NMR (100 MHz): δ 145.6, 144.2, 141.4, 138.9, 130.2, 129.2, 128.8, 127.7, 127.5, 126.7, 118.9, 114.6, 59.9, 44.5, MS, m/z (%): 183 (15), 182 ([M-MeO 2 SPhCH 2 ] +, 100), 104 (21), 77 (8). Anal. Calcd for C 21 H 21 NO 2 S: C, 71.76; H, 6.02; N, Found: C, 68.91; H, 5.84; N, Benzhydrylpyrrolidine (3a) 9 : Pale yellow solid. m = 1.76 g (74%). mp C. ATR-FTIR (neat, cm -1 ): 3026, 2973, 1487, 1451, 743, H NMR (400 MHz): δ 7.64 (d, J = 7.5 Hz, 4H), 7.41 (t, J = 7.5 Hz, 4H), 7.31 (t, J = 7.3 Hz, 2H), 4.33 (s, 1H), 2.60 (br s, 4H), 1.93 (br s, 4H). 13 C NMR (100 MHz): δ 144.5, 128.5, 127.6, 126.9, 76.7, 53.8, MS, m/z (%): 237 (M +, 5), 168 (8), 167 (33), 166 (9), 165 (29), 161 (12), 160 ([M-C 6 H 5 ] +, 100), 152 (15), 91 (11), 70 (12). Anal. Calcd for C 17 H 19 N: C, 86.03; H, 8.07; N, Found: C, 86.02; H, 8.04; N, Benzhydrylthiomorpholine (3b)*: Pale brown solid. m = 2.10 g (78%). mp C. ATR-FTIR (neat, cm -1 ): 3026, 2952, 1489, 1449, 1286, 949, 818, 745, 705, H NMR (400 MHz): δ 7.45 (d, J = 7.5 Hz, 4H), 7.34 (t, J = 7.5 Hz, 4H), 7.25 (t, J = 7.2 Hz, 2H), 4.46 (s, 1H), 2.75 (br s, 8H). 13 C NMR (100 MHz): δ 142.3, 128.6, 128.1, 127.0, 76.0, 53.7, MS, m/z (%): 269 (M +, 10), 242 (10), 241 (66), 208 (13), 193 (6), 192 (33), 168 (14), 167 ([M-C 4 H 8 NS] +, 100), 166 (19), 167 (77), 164 (13), 153 (7), 152 (38), 115 (8), 102 (13), 91 (7). Anal. Calcd for C 17 H 19 NS: C, 75.79; H, 7.11; N, Found: C, 75.96; H, 7.16; N, [(4-Methoxyphenyl)(phenyl)methyl]piperidine (3c) 1 : Pale yellow solid. m = 2.11 g (75%). mp C. ATR-FTIR (neat, cm -1 ): 3017, 2936, 1609, 1510, 1450, 1244, 1178, 1104, 1037, 763, 737, H NMR (400 MHz): δ 7.46 (d, J = 7.4 Hz, 2H), (m, 4H), 7.21 (t, J = 7.3 Hz, 1H), 6.87 (d, J = 8.7 Hz, 2H), 4.25 (s, 1H), 3.79 (s, 3H), (m, 4H), (m, 4H), (m, 2H). 13 C NMR (100 MHz): δ 158.4, 143.7, 135.4, 129.0, 128.4, 127.9, 126.6, 113.7, 76.0, 55.2, 53.2, 26.3, MS, m/z (%): 281 (M +, 15), 204 (20), 198 (17), 197 ([M-C 5 H 10 N] +, 100), 182 (11), 167 (5), 166 (7), 165 (16), 154 (7), 153 (11), 152 (6). Anal. Calcd for C 19 H 23 NO: C, 81.10; H, 8.24; N, Found: C, 80.92; H, 8.54; N, S10

11 4-[Phenyl(thiophen-3-yl)methyl]morpholine (3d)*: Pale yellow solid. m = 2.07 g (80%). mp C. ATR-FTIR (neat, cm -1 ): 2955, 2851, 2804, 1449, 1303, 1268, 1254, 1224, 1111, 1008, 873, 785, 768, 719, H NMR (400 MHz): δ 7.49 (d, J = 7.5 Hz, 2H), 7.35 (t, J = 7.5 Hz, 2H), (m, 3H), 7.15 (d, J = 4.7 Hz, 1H), 4.44 (s, 1H), 3.76 (t, J = 4.5 Hz, 4H), (m, 4H). 13 C NMR (100 MHz): δ 143.3, 141.7, 128.6, 128.2, (2 peaks), 125.9, 122.0, 71.8, 67.3, MS, m/z (%): 259 (M +, 6), 182 (18), 175 (11), 174 (49), 173 ([M-C 4 H 8 NO] +,100), 172 (8), 171 (17), 129 (35), 128 (8), 86 (29). Anal. Calcd for C 15 H 17 NOS: C, 69.46; H, 6.61; N, Found: C, 69.15; H, 6.67; N, [Benzo[1,3]dioxol-5-yl(4-fluorophenyl)methyl]piperazine-1-carbaldehyde (3e)*: Pale brown solid. m = 2.40 g (70%). mp C. ATR-FTIR (neat, cm -1 ): 2961, 2871, 2820, 1667, 1504, 1484, 1437, 1242, 1217, 1195, 1038, 995, 839, 818, H NMR (400 MHz): δ 7.87 (s, 1H), (m, 2H), 6.86 (t, J = 8.5 Hz, 2H), 6.79 (s, 1H), 6.70 (d, J = 7.9 Hz, 1H), 6.59 (d, J = 7.9 Hz, 1H), 5.77 (d, J = 8.9 Hz, 2H), 4.07 (s, 1H), 3.42 (br s, 2H), 3.24 (t, J = 4.4 Hz, 2H), (m, 4H). 13 C NMR (100 MHz): δ (d, J = Hz), 160.7, 148.0, 146.8, (d, J = 3.1 Hz), 135.8, (d, J = 7.9 Hz), 121.1, (d, J = 21.3 Hz), 108.2, 107.6, 101.0, 74.5, 52.1, 51.0, 45.7, F NMR (376 MHz): δ MS, m/z (%): 342 (M +, 6), 230 (23), 229 ([M-C 5 H 9 N 2 O] +,100), 199 (24), 172 (8), 171 (47), 170 (34). Anal. Calcd for C 19 H 19 FN 2 O 3 : C, 66.66; H, 5.59; N, Found: C, 66.27; H, 5.69; N, (4-Isopropylbenzyl)piperidine (3f)*: Colourless oil. m = 1.78 g (82%). ATR-FTIR (neat, cm -1 ): 2932, 1512, 1344, 1153, N 1113, 1039, 995, 862, 818, H NMR (400 MHz): δ 7.16 (AB, J = 8.1 Hz, 2H), 7.09 (AB, J = 8.1 Hz, 2H), 3.37 (s, 2H), 2.81 (hept, J = 6.9 Hz, 1H), 2.30 (br s, 4H), (m, 4H), (m, 2H), 1.17 (d, J = 6.9 Hz, 6H). 13 C NMR (100 MHz): δ 147.5, 135.8, 129.3, 126.1, 63.6, 54.5, 33.8, 25.9, 24.4, MS, m/z (%): 218 ([M+1] +, 17), 217 (M, 59), 216 ([M-1] +, 100), 174 (11), 134 (8), 133 (65), 118 (6), 117 (17), 115 (9), 105 (21), 98 (13), 92 (8), 91 (17), 84 (54), 56 (6). Anal. Calcd for C 15 H 23 N: C, 82.89; H, 10.67; N, Found: C, 82.54; H, 10.63; N, N-[2-(naphtalen-2-yl)-1-phenylethyl]aniline (4a)*: Colourless viscous oil. m = 1.82 g (56%). ATR-FTIR (neat, cm -1 ): 3408, 3051, 1600, 1502, 1315, 1266, 816, 745, H NMR (400 MHz): δ (m, 3H), 7.72 (s, 1H), (m, 10H), 6.78 (t, J = 7.3 Hz, 1H), 6.64 (dd, J = 8.6 Hz, J = 0.9 Hz, 2H), 4.85 (dd, J = 8.1 Hz, J = 5.8 Hz, 1H), 4.36 (s, 1H), 3.43 (dd, J = 14.0 Hz, J = 5.7 Hz, 1H), 3.31 (dd, J = 14.0 Hz, J = 8.2 Hz, 1H). 13 C NMR (100 MHz): δ 147.3, 143.5, 135.3, 133.6, 132.5, 129.2, 128.8, 128.4, 128.0, 127.8, 127.7, 127.6, 127.3, 126.6, 126.3, 125.8, 117.7, 113.9, 59.2, MS, m/z (%): 183 (15), 182 ([M-NaphtCH 2 ] +, 100), 104 (18), 77 (8). Anal. Calcd for C 24 H 21 N: C, 89.12; H, 6.54; N, Found: C, 85.94; H, 6.46; N, S11

12 Ethyl 3-phenyl-3-(phenylamino)propanoate (4b) 10 : Pale yellow solid. m = 1.48 g (55%). mp C. ATR-FTIR (neat, cm -1 ): 3384, 3025, 2980, 2925, 1712, 1602, 1218, 760, H NMR (400 MHz): δ (m, 5H), 7.14 (t, J = 7.6 Hz, 2H), 6.71 (t, J = 7.3 Hz, 1H), 6.60 (d, J = 7.8 Hz, 2H), 4.87 (t, J = 6.7 Hz, 1H), 4.64 (br s, 1H), 4.14 (q, J = 7.1 Hz, 2H), (m, 2H), 1.23 (t, J = 7.1 Hz, 3H). 13 C NMR (100 MHz): δ 171.2, 146.8, 142.2, 129.2, 128.8, 127.5, 126.3, 117.8, 113.7, 60.8, 55.0, 42.9, MS, m/z (%): 269 (M +, 20), 183 (14), 182 ([M-CH 2 CO 2 Et] +, 100), 180 (9), 104 (17), 77 (6). Anal. Calcd for C 17 H 19 NO 2 : C, 75.81; H, 7.11; N, Found: C, 75.65; H, 7.05; N, N-(1-phenylbut-3-enyl)aniline (4c) 11 : Pale yellow oil. m = 1.12 g (50%). ATR-FTIR (neat, cm -1 ): 3411 (NH), 3023, 2977, 2912, 1639, 1503, 1315, 1266, 993, 918, 747, H NMR (400 MHz): δ (m, 4H), 7.38 (t, J = 7.2 Hz, 1H), 7.23 (t, J = 7.4 Hz, 2H), 6.80 (t, J = 7.3 Hz, 1H), 6.66 (d, J = 7.9 Hz, 2H), (m, 1H), (m, 2H), 4.60 (dd, J = 7.1 Hz, J = 5.9 Hz, 1H), 4.31 (br s, 1H), (m, 1H), (m, 1H). 13 C NMR (100 MHz): δ 147.5, 143.7, 134.8, 129.2, 128.7, 127.1, 126.4, 118.5, 117.5, 113.6, 57.3, MS, m/z (%): 223 (M +, 6), 183 (16), 182 ([M-CH 2 CH=CH 2 ] +,100), 180 (8), 104 (39), 77 (13). Anal. Calcd for C 16 H 17 N: C, 86.05; H, 7.67; N, Found: C, 85.67; H, 7.63; N, (1-Phenylbut-2-enyl)piperidine (4d)*, (Z + E) mixture: Pale yellow oil. m = 1.75 g (81%). ATR-FTIR (neat, cm -1 ): 3024, 2931, 1489, 1450, 755, 716, H NMR (400 MHz): δ (m, 4H), (m, 1H), (m, 2H), 3.92 (d, J = 8.8 Hz, 0.78H), (m, 0.24H), (m, 4H), (m, 3H), (m, 4H), (m, 2H). 13 C NMR (100 MHz): δ 143.1, 133.4, 132.7, 128.4, 128.3, 128.0, 127.9, 126.8, 126.7, 125.1, 74.7, 67.7, 52.6, 52.5, 26.2, 24.8, 24.7, 17.9, MS, m/z (%) for the major diastereoisomer: 216 ([M+1] +, 5), 215 (M +, 21), 214 ([M-1] +, 28), 201 (5), 200 (37), 175 (7), 174 (54), 139 (9), 138 ([M-C 6 H 5 ] +, 100), 132 (6), 131 (58), 130 (74), 129 (30), 128 (11), 117 (9), 116 (13), 115 (17), 92 (6), 91 (47), 85 (11), 84 (34). Anal. Calcd for C 15 H 21 N: C, 83.67; H, 9.83; N, Found: C, 82.05; H, 9.89; N, S12

13 References: (1) Le Gall, E.; Troupel, M.; Nedelec, J. -Y. Tetrahedron 2006, 62, (2) Hatano, B.; Nagahashi, K.; Kijima, T. J. Org. Chem. 2008, 73, (3) Fan, R.; Pu, D.; Qin, L.; Wen, F.; Yao, G.; Wu, J. J. Org. Chem. 2007, 72, (4) Bytschkov, I.; Doye, S. Eur. J. Org. Chem. 2001, (5) Heutling, A.; Doye, S. J. Org. Chem. 2002, 67, (6) Yasuda, M.; Hamasuna, S.; Yamano, K.; Kubo, J.; Shima, K. Heterocycles 1992, 34, (7) Hoover, D. J.; Wester, R. T.; Rosati, R. L. Eur. Pat. Appl. EP (1988); Chem. Abstr., 110, (1989). (8) Horillo-Martinez, P.; Hultzsch, K. C.; Gil, A.; Branchadell, V. Eur. J. Org. Chem. 2007, (9) Sezen, B.; Sames, D. J. Am. Chem. Soc. 2005, 127, (10) Saidi, M. R.; Azizi, N.; Zali-Boinee, H. Tetrahedron 2001, 57, (11) Deng, D.-S.; Liu, P.; Cai, J. Eur. J. Org. Chem. 2007, S13

14 S14 1 H NMR spectrum of compound 1a

15 S15 13 C NMR spectrum of compound 1a

16 S16 1 H NMR spectrum of compound 1b

17 S17 13 C NMR spectrum of compound 1b

18 S18 1 H NMR spectrum of compound 1c

19 S19 13 C NMR spectrum of compound 1c

20 S20 1 H NMR spectrum of compound 1d

21 S21 13 C NMR spectrum of compound 1d

22 S22 1 H NMR spectrum of compound 1e

23 S23 13 C NMR spectrum of compound 1e

24 S24 1 H NMR spectrum of compound 1f

25 S25 13 C NMR spectrum of compound 1f

26 S26 1 H NMR spectrum of compound 1g

27 S27 13 C NMR spectrum of compound 1g

28 S28 1 H NMR spectrum of compound 1h

29 S29 13 C NMR spectrum of compound 1h

30 S30 1 H NMR spectrum of compound 1i

31 S31 13 C NMR spectrum of compound 1i

32 S32 19 F NMR spectrum of compound 1i

33 S33 1 H NMR spectrum of compound 1j

34 S34 13 C NMR spectrum of compound 1j

35 S35 1 H NMR spectrum of compound 1k

36 S36 13 C NMR spectrum of compound 1k

37 S37 19 F NMR spectrum of compound 1k

38 S38 1 H NMR spectrum of compound 1l

39 S39 13 C NMR spectrum of compound 1l

40 S40 1 H NMR spectrum of compound 1m

41 S41 13 C NMR spectrum of compound 1m

42 S42 1 H NMR spectrum of compound 1n

43 S43 13 C NMR spectrum of compound 1n

44 S44 1 H NMR spectrum of compound 1o

45 S45 13 C NMR spectrum of compound 1o

46 S46 1 H NMR spectrum of compound 2a

47 S47 13 C NMR spectrum of compound 2a

48 S48 1 H NMR spectrum of compound 2b

49 S49 13 C NMR spectrum of compound 2b

50 S50 19 F NMR spectrum of compound 2b

51 S51 1 H NMR spectrum of compound 2c

52 S52 13 C NMR spectrum of compound 2c

53 S53 1 H NMR spectrum of compound 2d

54 S54 13 C NMR spectrum of compound 2d

55 S55 1 H NMR spectrum of compound 2e

56 S56 13 C NMR spectrum of compound 2e

57 S57 1 H NMR spectrum of compound 2f

58 S58 13 C NMR spectrum of compound 2f

59 S59 1 H NMR spectrum of compound 2g

60 S60 13 C NMR spectrum of compound 2g

61 S61 1 H NMR spectrum of compound 2h

62 S62 13 C NMR spectrum of compound 2h

63 S63 19 F NMR spectrum of compound 2h

64 S64 1 H NMR spectrum of compound 2i

65 S65 13 C NMR spectrum of compound 2i

66 S66 1 H NMR spectrum of compound 2j

67 S67 13 C NMR spectrum of compound 2j

68 S68 1 H NMR spectrum of compound 3a

69 S69 13 C NMR spectrum of compound 3a

70 S70 1 H NMR spectrum of compound 3b

71 S71 13 C NMR spectrum of compound 3b

72 S72 1 H NMR spectrum of compound 3c

73 S73 13 C NMR spectrum of compound 3c

74 S74 1 H NMR spectrum of compound 3d

75 S75 13 C NMR spectrum of compound 3d

76 S76 1 H NMR spectrum of compound 3e

77 S77 13 C NMR spectrum of compound 3e

78 S78 19 F NMR spectrum of compound 3e

79 S79 1 H NMR spectrum of compound 3f

80 S80 13 C NMR spectrum of compound 3f

81 S81 1 H NMR spectrum of compound 4a

82 S82 13 C NMR spectrum of compound 4a

83 S83 1 H NMR spectrum of compound 4b

84 S84 13 C NMR spectrum of compound 4b

85 S85 1 H NMR spectrum of compound 4c

86 S86 13 C NMR spectrum of compound 4c

87 S87 1 H NMR spectrum of compound 4d

88 S88 13 C NMR spectrum of compound 4d

89 Chromatogram of compound 1f Varian 3400, SGE BP1 5m column, S89

90 Chromatogram of compound 1k Varian 3400, SGE BP1 5m column, S90

91 Chromatogram of compound 1l Varian 3400, SGE BP1 5m column, S91

92 Chromatogram of compound 1o Varian 3400, SGE BP1 5m column, S92

93 Chromatogram of compound 2i Varian 3400, SGE BP1 5m column, S93

94 Chromatogram of compound 2j Varian 3400, SGE BP1 5m column, S94

95 Chromatogram of compound 4a Varian 3400, SGE BP1 5m column, S95

96 Chromatogram of compound 4d (Z + E mixture) Varian 3400, SGE BP1 5m column, S96