Sequential catalysis for the production of sterically hindered amines: Ruthenium(II)-catalyzed C-H bond activation and hydrosilylation of imines

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1 Electronic Supporting Information Sequential catalysis for the production of sterically hindered amines: Ruthenium(II)-catalyzed C- bond activation and hydrosilylation of imines Bin Li, Charles B. Bheeter, Christophe Darcel, Pierre. Dixneuf Institut Sciences Chimiques de Rennes Team Catalysis and Organometallics Université de Rennes 1 Campus de Beaulieu REES cedex, rance ax: (+) Table of Contents S2 S2 S5 General remarks General procedures for arylation and hydrosilylation reactions Characterization data of substrates

2 General remarks All reagents were obtained from commercial sources and used as received. MP, Toluene and T was distilled under conventional methods (Ca 2 or sodium, benzophenone), and stored under an argon atmosphere. All reactions were carried out under argon atmosphere. Technical grade petroleum ether (40-60 C bp.) and ethyl acetate were used for chromatography column. 1 MR spectra were recorded in CDCl 3 at ambient temperature on Bruker DPX-200, AVACE I 300 spectrometers at 200.1, and Mz, respectively, using the solvent as internal standard (7.26 ppm). 13 C MR spectra were obtained at 50 or 75 Mz and referenced to the internal solvent signals (central peak is 77.0 ppm). Chemical shift ( ) and coupling constants (J) are given in ppm and in z, respectively. The peak patterns are indicated as follows: (s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet, and br. for broad). GC analyses were performed with GC-2014 (Shimadzu) 2010 equipped with a 30-m capillary column (Supelco, SPBTM-20, fused silica capillary column, 30 M*0.25 mm*0.25 mm film thickness), was used with 2 /air as vector gas. GCMS were measured by GCMS-QP2010S (Shimadzu) with GC-2010 equipped with a 30-m capillary column (Supelco, SLBTM-5ms, fused silica capillary column, 30 M*0.25 mm*0,25 mm film thickness), was used with helium as vector gas. The following GC conditions were used: Initial temperature 100 C, for 2 minutes, then rate 10 C/min. until 250 C and 250 C for 25 minutes. General procedure for arylation in MP at 160 C In a typical experiment, [RuCl 2 (p-cymene)] 2 (0.025 mmol, 15.3 mg), KOAc (0.1 mmol, 9.8 mg) and K 2 CO 3 (1.5 mmol, 207 mg) were introduced in dried Schlenck tube under argon, equipped with magnetic stirring bar. -Benzylidenetoluidine (0.5 mmol, 97.6 mg), bromobenzene (1.25 mmol, 125 µl), MP (2 ml) and tetradecane (10 μl) as an internal standard were added in the Schlenck tube which was then placed in the oil bath at 160 o C. The resulting mixture was allowed to stir for the specified time. Then, the reaction conversion was analyzed by gas chromatography. The reaction mixture was diluted with 30 ml of diethyl ether, washed with water (20 ml 3), and dried over MgSO 4. Then the solvent was evaporated under vacuum and desired product was isolated by flash chromatography on neutral alumina, by using a mixture of petroleum ether / ethyl acetate (9.5:0.5) as eluent. The product was obtained and the mono and diarylated product ratio was determined by 1 MR. General procedure for arylation in MP using Oi type conditions In a typical experiment, [RuCl 2 (p-cymene)] 2 ( mmol, 3.9 mg), KOAc ( mmol, 1.3 mg), PPh 3 ( mmol, 3.3 mg) and K 2 CO 3 (1 mmol, 138 mg) were introduced in dried Schlenck tube under argon, equipped with magnetic stirring bar. - Benzylidenetoluidine (0.25 mmol, 49 mg), bromobenzene (0.75 mmol, 75 µl), MP (2 ml) and tetradecane (10 μl) as an internal standard were added in the Schlenck tube which was then placed in the oil bath at required temperature (100 o C, 120 o C). The resulting mixture was allowed to stir for the specified time. The reaction conversion was

3 then analyzed by gas chromatography. The reaction mixture was diluted with 30 ml of diethyl ether, washed with water (20 ml 3), and dried over MgSO 4. The solvent was evaporated under vacuum and the desired product was purified by flash chromatography on neutral alumina using a mixture of petroleum ether / ethyl acetate (9.5:0.5) as eluent. The product was obtained and the mono and diarylated products ratio was determined by 1 MR. General procedure for Ruthenium catalyzed sequential Arylation/ydrosilylation In a typical experiment, [RuCl 2 (p-cymene)] 2 ( mmol, 3.9 mg), KOAc ( mmol, 1.3 mg), PPh 3 ( mmol, 3.3 mg) and K 2 CO 3 (1 mmol, 138 mg) were introduced in dried Schlenck tube under argon, equipped with magnetic stirring bar. - Benzylidenetoluidine (0.25 mmol, 49 mg), bromobenzene (0.75 mmol, 75 µl), MP (2 ml) and tetradecane (10 μl) as an internal standard were introduced in the Schlenck tube which was then placed in the oil bath at 100 o C. The resulting mixture was allowed to stir for 20 h. The reaction mixture was diluted with 30 ml of diethyl ether, quickly washed with water (20 ml 3), and dried over MgSO 4. The solvent was then evaporated under vacuum. The mixture was quickly purified by filtratio on a short column of alumina using a mixture of petroleum ether / ether acetate (9.5:0.5) as eluent. After evaporation of the solvent, to the mixture was added [RuCl 2 (p-cymene)] 2 ( mmol, 3.9 mg), diphenylsilane (0.5 mmol, 46 µl) and diethyl ether (1 ml) under argon and the resulting mixture was stirred at ambient temperature. After 16 h, methanol (1 ml) was slowly added to the reaction mixture, which was stirred for 0.5 h and 2 M aqueous ao (5 ml) was added to reaction mixture, which was stirred at room temperature for 3 h. The reaction product was extracted with diethyl ether (50 ml 3), and the diethyl ether solution was dried over anhydrous MgSO 4. The desired product was isolated by flash chromatography on silica using a mixture of petroleum ether / ethyl acetate (9.8:0.2) as eluaent. The product was obtained and the mono and diarylated products ratio was determined by 1 MR. General procedure for Ruthenium catalyzed ydrosilylation In a typical experiment, [RuCl 2 (p-cymene)] 2 ( mmol, 3.9 mg), - Benzylidenetoluidine (0.25 mmol, 49 mg), diphenylsilane (0.5 mmol, 46 μl) and diethyl ether (1 ml) were introduced in dried Schlenck tube under argon,. The reaction mixture was stirred at ambient temperatura for 16 h. Methanol (1 ml) was then slowly added to the reaction mixture, which was stirred for 0.5 h. 2 M aqueous ao (5 ml) was then added to reaction mixture, which was stirred at room temperature for 3 h. Then, the conversion of the reaction was analyzed by 1 MR.

4 -Benzylidenetoluidine 1a 1,2 Characterizations of the substrates Greenish yellow solid, yield = 90%, 1 MR (200 Mz, CDCl 3 ): δ = 8.50 (s, 1), (m, 2), (m, 3), (m, 4), 2.40 (s, 3). GC: A t = 12.5 min. MS (EI): m/z: 194 (100, M + - ), 193 (60), 107 (20), 91 (21). -(p-methylbenzylidene)toluidine 1b 2 White solid, yield = 95%, 1 MR (200 Mz, CDCl 3 ): δ = 8.45 (s, 1), 7.81 (d, 2, J = 8.1 z), (m, 6), 2.44 (s, 3), 2.39 (s, 3) GC: A t = 12.1 min. MS (EI): m/z: 208 (100, M + - ), 195 (60), 121 (20), 91 (21). 3 C -(p-methoxybenzylidene)toluidine 1c Pale white solid, yield = 88%, 1 MR (200 Mz, CDCl 3 ): δ = 8.42 (s, 1), 7.86 (d, 2, J = 8.8 z), (m, 6), 3.89 (s, 3), 2.39 (s, 3). GC: A t = 13.2 min. MS (EI): m/z: 224 (100, M + - ), 223 (60), 134 (24), 91 (21). 3 CO 4-methoxy--benzylidenaniline 1d 3 O Pale white solid, yield = 85%, 1 MR (200 Mz, CDCl 3 ): δ = 8.51 (s, 1), (m, 2), (m, 3), 7.26 (d, 2, J = 8.6 z), 6.96 (d, 2, J = 8.6 z), 3.86 (s, 3). GC: A t = 15.5 min. MS (EI): m/z: 210 (100, M + - ), 209 (67), 108 (21), 104 (19). -(4-chlorobenzylidene)-p-toluidine 1e Cl White solid, yield = 79%, 1 MR (200 Mz, CDCl 3 ): δ = 8.45 (s, 1), 7.86 (d, 2, J = 8.5 z), 7.47 (d, 2, J = 8.4 z), 7.23 (d, 2, J = 8.3 z), 7.16 (d, 2, J = 8.5 z), 2.40 (s, 3). 13 C MR (50 Mz, CDCl 3 ): δ = 157.9, 149.0, 137.1, 136.1, 134.8, , , 129.0, 120.8, 21.5; GC: A t = 15.0 min. MS (EI): m/z: 231 (26, M + ), 229 (80, M + ), 118 (20), 91 (100), 77 (10), 65 (68). S4

5 -(1-phenylethylidene)-p-toluidine 1f 4 White solid, yield = 80%, 1 MR (200 Mz, CDCl 3 ): δ = (m, 2), (m, 3), 7.19 (d, 2, J = 8.0 z), 6.73 (d, 2, J = 8.0 z), 2.38 (s, 3), 2.27 (s, 3). GC: A t = 11.9 min. MS (EI): m/z: 208 (100, M + - ), 195 (60), 121 (20), 91 (21). -[1-(p-tolyl)ethylidene)-p-toluidine 1g Pale green solid, yield = 70%, 1 MR (200 Mz, CDCl 3 ): δ = 7.89 (d, 2, J = 8.1 z), 7.26 (d, 2, J = 8.1 z), 7.17 (d, 2, J = 8.1 z), 6.32 (d, 2, J = 8.1 z), 2.43 (s, 3), 2.37 (s, 3), 2.23 (s, 3). GC: A t = 12.9 min. MS (EI): m/z: 222 (100%, M + - ), 209 (60%), 119 (17%), 91 (21%). -[1-(p-methoxyphenyl)ethylidene)-p-toluidine 1h 3 CO Pale green solid, yield = 79%, 1 MR (200 Mz, CDCl 3 ): δ = 7.96 (d, 2, J = 8.8 z), 7.17 (d, 2, J = 8.0 z), 6.97 (d, 2, J = 8.8 z), 6.71 (d, 2, J = 8.0 z), 3.88 (s, 3), 2.37 (s, 3), 2.22 (s, 3). GC: A t = 14.7 min. MS (EI): m/z: 238 (100%, M + - ), 224 (56%), 148 (17%), 91 (21%). 4-methoxy--(1-phenylidene)aniline 1i 4 O Yellowish orange solid, yield = 80%, 1 MR (200 Mz, CDCl 3 ): δ = (m, 2), (m, 3), 6.93 (d, 2, J = 8.7 z), 6.80 (d, 2, J = 8.7 z), 3.82 (s,3), 2.25 (s, 3). GC: A t = 15.9 min. MS (EI): m/z: 224 (100, M + - ), 210 (47), 118 (25), 108 (16). -(p-nitrobenzylidene)toluidine 1j O 2 Yellowish orange solid, yield = 90%, 1 MR (200 Mz, CDCl 3 ): δ = 8.60 (s, 1), 8.35 (d, 2, J = 8.6 z), 8.08 (d, 2, J = 8.6 z), (m, 4), 2.42 (s, 3). GC: A t = 9.15 min. MS (EI): m/z: 240 (100%, M + ), 193 (45), 152 (10), 118 (34), 91 (82), 65 (55), 51 (15). S5

6 -[(o,o -diphenyl)benzylidene]-p-toluidine 4a Green solid, yield = 75%, 1 MR (200 Mz, CDCl 3 ): δ = 8.36 (s, 1), (m, 13), 7.10 (d, 2, J = 8.2 z), 6.62 (d, 2, J = 8.1 z), 2.33 (s, 3). 13 C MR (50 Mz, CDCl 3 ): δ = 161.0, 150.0, 143.0, 141.5, 135.7, 134.3, 130.5, 130.2, 129.9, 129.5, 128.5, 127.5, 120.6, GC: t R = 30.5 min. MS (EI): m/z: 346 (100, M + - ), 254 (16), 241 (15), 91 (10), 65 (11); RMS (ESI): m/z calcd for C (M+ + ) , found [(o,o -diphenyl)-p-methylbenzylidene]-p-toluidine 4b Green solid, yield = 65%, 1 MR (300 Mz, CDCl 3 ): δ = 8.27 (s, 1), (m, 12), 7.03 (d, 2, J = 8.1 z), 6.55 (d, 2, J = 8.1 z), 2.48 (s, 3), 2.28 (s, 3). 13 C MR (75 Mz, CDCl 3 ): δ = 160.4, 142.6, 141.2, 139.0, 135.1, 130.5, 129.9, 129.5, 129.4, 128.1, 127.9, 126.9, 120.2, 21.4, GC: t R = 25.2 min. MS (EI): m/z: 360 (100, M + - ), 255 (10), 91 (10), 65 (10); RMS (ESI): m/z calcd for C (M+ + ) , found [(o,o -diphenyl)-p-methoxylbenzylidene]-p-toluidine 4c 3 CO Orange solid, yield = 68%, 1 MR (200 Mz, CDCl 3 ): δ = 8.23 (s, 1), (m, 10), 7.01 (d, 2, J = 8.0 z), 6.97 (s, 2), 6.54 (d, 2, J = 8.0 z), 3.92 (s, 3), 2.28 (s, 3). 13 C MR (50 Mz, CDCl 3 ): δ = 159.7, 159.5, 149.8, 144.5, 141.1, 134.9, 129.8, 129.3, 127.9, 127.1, 126.6, 120.1, 115.2, 55.5, GC: t R = 29.4 min. MS (EI): m/z: 377 (32, M + ), 376 (100), 333 (18), 271 (10), 91 (10), 65 (10). RMS (ESI): m/z calcd for C O (M+ + ) , found [(o,o -di-(4-tolyl)benzylidene]-p-toluidine 4d Yellow oil, yield = 51%, 1 MR (200 Mz, CDCl 3 ): δ = 8.33 (s, 1), (m, 11), 7.07 (d, 2, J = 8.1 z), 6.63 (d, 2, J = 8.1 z), 2.42 (s, 6), 2.31 (s, 3). 13 C MR (75 Mz, CDCl 3 ): δ = 160.9, 149.9, 142.4, 138.1, 136.6, 135.0, 133.8, 129.9, 129.5, 129,4, 128.9, 128.7, 120.1, 21.2, GC: t R = 35.5 min. MS (EI): m/z (relative intensity) 375 (30, M + ), 374 (100), 358 (5), 282 (5), 269 (10), 91(5), 51 (5). RMS (ESI): m/z calcd for C (M+ + ) , found S6

7 -[(o,o -di(4-fluorophenyl)benzylidene]-p-toluidine 4e Orange solid, yield = 55%, 1 MR (200 Mz, CDCl 3 ): δ = 8.28 (s, 1), (m, 7), (m, 6), 6.60 (d, 2, J = 8.0 z), 2.31 (s, 3). 13 C MR (75 Mz, CDCl 3 ): δ = (d, J C = 245 z), 159.9, 149.3, 141.6, (d, J C = 3.3 z), 135.7, 133.9, (d, J C = 8 z), 129.9, 129.6, 129.1, 120.1, (d, J C = 21 z), MR (188 Mz, CDCl 3 ): δ = GC: t R = 20.5 min. MS (EI): m/z: 382 (100, M + - ), 290 (10), 277 (15), 91 (10), 65 (15). RMS (ESI): m/z calcd for C (M+ + ) , found [(o,o -di(4-methoxyphenyl)benzylidene]-p-toluidine 4f OMe Yellow oil, yield = 52%, 1 MR (200 Mz, CDCl 3 ): δ = 8.32 (s, 1), (m, 7), 7.06 (d, 2, J = 8.1 z), 6.96 (d, 4, J = 8.3 z), 6.65 (d, 2, J = 8.1 z), 3.87 (s, 6), 2.31 (s, 3). 13 C MR (75 Mz, CDCl 3 ): δ = 161.0, 158.8, 149.8, 142.1, 135.2, 133.8, 133.5, 131.2, 129.5, 128.9, 127.7, 120.2, 113.5, 55.3, RMS (ESI): m/z calcd for C O 2 (M+ + ) , found OMe -[(o,o -diphenyl)benzylidene]-p-methoxyaniline 4h OMe white solid, yield = 71%, 1 MR (200 Mz, CDCl 3 ): δ = 8.34 (s, 1), (m, 13), 6.80 (d, 2, J = 8.8 z), 6.64 (d, 2, J = 8.8 z), 3.78 (s, 3). 13 C MR (50 Mz, CDCl 3 ): δ = 159.8, 158.3, 145.6, 143.0, 141.6, 134.3, 130.4, 130.1, 129.4, 128.4, 127.4, 122.0, 114.5, GC: t R = 31.0 min. MS (EI): m/z (relative intensity) 362 (100, M + - ), 318 (12), 241 (20). RMS (ESI): m/z calcd for C O (M+ + ) , found [(o,o -diphenyl)-p-chlorobenzylidene]-p-toluidine 4i Cl Light yellow solid, yield = 88%, 1 MR (200 Mz, CDCl 3 ): δ = 8.27 (s, 1), (m, 12), 7.06 (d, 2, J = 8.0 z), 6.58 (d, 2, J = 8.0 z), 2.32 (s, 3). 13 C MR (50 Mz, CDCl 3 ): δ = 159.2, 149.3, 144.2, 139.8, 135.5, 134.6, 132.3, 129.6, 129.5, 128.2, 127.5, 120.1, 110.1, GC: t R = 32.0 min. MS (EI): m/z (relative intensity) 383 (10, M + ), 382 (33), 381 (30, M + ), 380 (100), 275 (10), 253 (10), 239 (15), 91(15), 65 (20). RMS (ESI): m/z calcd for C Cl (M + + ) , found S7

8 -[(o,o -di(4-acetylphenyl)benzylidene]-p-toluidine 4j O Yellow solid, yield = 63%, 1 MR (200 Mz, CDCl 3 ): δ = 8.31 (s, 1), 8.03 (d, 4, J = 8.2 z), (m, 7), 7.04 (d, 2, J = 8.1 z), 6.56 (d, 2, J = 8.1 z), 2.67 (s, 6), 2.30 (s, 3). 13 C MR (50 Mz, CDCl 3 ): δ = 197.8, 159.0, 149.0, 145.8, 141.7, 135.9, 135.7, 133.5, 130.2, 130.1, 129.6, 129.4, 128.1, 120.0, 26.7, RMS (ESI): m/z calcd for C O 2 (M + + ) , found O -{1-[o,o -(diphenyl)phenyl]ethylidene}-p-toluidine 5a Yellow solid, yield = 70%, 1 MR (200 Mz, CDCl 3 ): E:Z = 9:1 δ = (m, 14.5), 7.06 (d, 2, J = 7.5 z), 6.85 (d, 0.2, J = 7.5 z), 6.30 (d, 0.2, J = 7.5 z), 6.24 (d, 2, J = 7.5 z), 2.32 (s, 3), 2.19 (s, 0.3), 1.60 (s, 3.3). 13 C MR (50 Mz, CDCl 3 ): δ = 170.1, 148.2, 141.4, 140.4, 140.0, 132.4, 129.4, , , 128.0, 127.8, 127.1, 118.5, 22.8, GC: t R = 29.6 min. MS (EI): m/z: 360 (100, M + - ), 346 (65), 330 (10), 254 (16), 132 (17), 91 (32), 65 (25). RMS (ESI): m/z calcd for C (M+ + ) , found {1-[o,o -(diphenyl)-p-tolyl]ethylidene}-p-toluidine 5b 3 C White solid, yield = 60%, 1 MR (200 Mz, CDCl 3 ): δ = (m, 12), 7.00 (d, 2, J = 8.1 z), 6.15 (d, 2, J = 8.0 z), 2.48 (s, 3), 2.27 (s, 3), 1.52 (s, 3). 13 C MR (50 Mz, CDCl 3 ): δ = 170.1, 148.3, 141.5, 140.0, 137.5, 132.3, 129.9, 129.4, 129.2, 128.2, 128.0, 127.0, 118.5, 22.9, 21.2, GC: t R = 25.8 min. MS (EI): m/z: 374 (100, M + - ), 360 (51), 344 (10), 269 (12), 132 (10), 91 (21), 65 (17). RMS (ESI): m/z calcd for C (M+ + ) , found {1-[o,o -(diphenyl)-p-methoxyphenyl]ethylidene}-p-toluidine 5c 3 CO White solid, yield = 63%, 1 MR (200 Mz, CDCl 3 ): δ = (m, 12), 7.02 (m, 2), 6.13 (d, 2, J = 7.8 z), 3.91 (s, 3), 2.27 (s, 3), 1.51 (s, 3). 13 C MR (75 Mz, CDCl 3 ): δ = 169.9, 158.5, 148.4, 141.6, 141.5, 132.3, 129.3, 129.2, 128.3, 128.0, 127.2, 118.5, 114.8, 55.5, 23.1, GC: t R = 33.6 min. MS (EI): m/z: 390 (100, M + - ), 376 (38), 333 (12), 285 (10), 91 (21), 65 (17). RMS (ESI): m/z calcd for C O (M+ + ) , found S8

9 -{1-[o,o -di(4-fluorophenyl)phenyl]ethylidene}-p-toluidine 5d White solid, yield = 81%, E:Z = 1:0.1; 1 MR (200 Mz, CDCl 3 ): δ = (m, 13.6), 7.04 (d, 2, J = 8.2 z), 6.82 (d, 0.2, J = 8.2 z), 6.25 (d, 0.2, J = 8.2 z), 6.19 (d, 2, J = 8.2 z), 2.29 (s, 3), 2.27 (s, 0.3), 2.10 (s, 0.3), 1.51 (s, 3). 13 C MR (75 Mz, CDCl 3 ): δ = 169.9, (d, J = 245 z), 147.9, 140.6, 139.0, (d, J = 3.3 z), 132.8, (d, J = 8 z), , 127.9, 118.5, (d, J = 21 z), 22.8, MR (188 Mz, CDCl 3 ): δ = GC: t R = 19.8 min. MS (EI): m/z: 398 (15, M + + ), 396 (100), 382 (94), 290 (15), 132 (20), 107(10), 91 (44), 65 (40). RMS (ESI): m/z calcd for C (M+ + ) , found {1-[o,o -di(4-t-butylphenyl)phenyl]ethylidene}-p-toluidine 5e t-bu White solid, yield = 78%, E:Z = 87:13; 1 MR (300 Mz, CDCl 3 ): δ = (m, 11.9), 7.34 (d, 0.6, J = 8.1 z), 7.11 (d, 0.6, J = 8.1 z), 6.98 (d, 2, J = 8.1 z), 6.73 (d, 0.3, J = 8.1 z), 6.19 (d, 0.3, J = 8.1 z), 6.09 (d, 2, J = 8.1 z), 2.27 (s, 3), 2.25 (s, 0.34), 2.07 (s, 0.34), 1.54 (s, 3), 1.41 (s, 18), 1.39 (s, 2.3). 13 C MR (75 Mz, CDCl 3 ): δ = 170.3, 150.0, 148.4, 140.8, 140.0, 138.6, 132.2, 129.1, , 127.7, 124.8, 118.5, 34.6, 31.4, 22.8, GC: t R = 52.5 min. MS (EI): m/z: 472 (100, M + - ), 458 (10), 187 (10), 132 (15), 91 t-bu (20), 57 (95). RMS (ESI): m/z calcd for C (M+ + ) , found {1-[o,o -di(p-tolyl)phenyl]ethylidene}-p-toluidine 5f Orange oil, yield = 56%, E:Z = 1:0.1; 1 MR (200 Mz, CDCl 3 ): δ = (m, 14.7), 6.80 (d, 0.2, J = 8.0 z), 6.23 (d, 2, J = 8.2 z), 2.45 (s, 6), 2.41 (s, 0.6), 2.29 (s, 3.3), 2.13 (s, 0.3), 1.56 (s, 3). 13 C MR (75 Mz, CDCl 3 ): δ = 170.3, 148.4, 140.5, 140.0, 138.6, 136.7, 132.4, 129.4, 129.3, 129.1, 128.7, 127.8, 118.6, 22.8, 21.2, GC: t R = 28.5 min. MS (EI): m/z: 389 (40), 388 (100, M + ), 374 (40), 358 (10), 283 (10), 132 (10), 91 (25), 65 (20). RMS (ESI): m/z calcd for C (M+ + ) , found S9

10 -{1-[o,o -(diphenyl)phenyl]ethylidene}-p-methoxyaniline 5g 5 White solid, yield = 74%, 1 MR (200 Mz, CDCl 3 ): E:Z = 1:0.17; δ = (m, 13), 6.76 (d, 2, J = 8.8 z), 6.55 O (d, 0.34, J = 8.8 z), 6.31 (d, 0.34, J = 8.8 z), 6.19 (d, 2, J = 8.7 z), 3.76 (s, 3.55), 2.10 (s, 0.51), 1.55 (s, 3). 13 C MR (50 Mz, CDCl 3 ): (E) δ = 170.3, 155.7, 144.0, 141.4, 140.5, 140.0, 129.4, 129.2, 128.2, 128.0, 127.1, 119.8, 114.0, 55.4, 22.8 GC: A t = 27.5 min. MS (EI): m/z: 377 (75, M + ), 376 (100), 362 (70), 346(10), 318 (15), 255 (20), 239 (12), 148 (16), 123 (14). RMS (ESI): m/z calcd for C O (M+ + ) , found {[2,6-di(4-tolyl)phenyl]methyl}-4-methylaniline 6a Light yellow solid, yield = 78%, 1 MR (200 Mz, CDCl 3 ): δ = (m, 11), 6.84 (d, 2, J = 8.3 z), 6.16 (d, 2, J = 8.3 z), 4.17 (s, 2), 3.39 (s, 1), 2.41 (s, 6), 2.18 (s, 3). 13 C MR (75 Mz, CDCl 3 ): δ = 145.3, 143.3, 138.6, 136.9, 134.2, 129.7, 129.3, 129.0, , 127.1, 126.5, 113.5, 43.7, 21.2, GC: t R = 22.7 min. MS (EI): m/z: 378 (25, M + + ), 377 (70, M + ), 271 (100), 256 (30), 241 (15), 179 (10), 120 (10), 107 (10), 91 (10), 77 (5), 65 (10). RMS (ESI): m/z calcd for C , found ; m/z calcd for C , found {[2,6-diphenyl)phenyl]methyl}-4-methylaniline 6b Yellow solid, yield = 82%, 1 MR (200 Mz, CDCl 3 ): δ = (m, 13), 6.82 (d, 2, J = 8.0 z), 6.12 (d, 2, J = 8.0 z), 4.16 (s, 2), 3.34 (s, 1), 2.17 (s, 3). 13 C MR (50 Mz, CDCl 3 ): δ = 145.3, 143.3, 141.5, 134.1, 129.7, 129.3, 129.1, 128.3, 127.3, 127.1, 126.4, 113.3, 43.6, GC: t R = 30.4 min. MS (EI): m/z: 350 (25, M + ), 349 (90), 346 (35), 243 (100), 228 (25), 165 (40), 115 (30), 107 (35), 91 (50), 77 (15), 65 (15). RMS (ESI): m/z calcd for C , found {[2,6-di(4-fluorophenyl)phenyl]methyl}-4-methylaniline 6c Yellow oil, yield = 76%, 1 MR (200 Mz, CDCl 3 ): δ = (m, 11), 6.76 (d, 2, J = 8.0 z), 6.19 (d, 2, J = 8.0 z), 4.06 (s, 2), 3.33 (s, 1), 2.20 (s, 3). 13 C MR (50 Mz, CDCl 3 ): δ = (d, J C = 246 z), 145.1, 142.2, (d, 2, J = 3.5 z), 134.2, (d, J C = 8.0 z), 130.0, 129.5, 127.3, 126.8, (d, J = 21.3 z), 113.2, 43.6, MR (188 Mz, CDCl 3 ): δ = GC: t R = 20.7 min. MS (EI): m/z: 385 (100, M + ), 279 (100), 259 (40), 239 (15), 183 (30), 133 (20), 120 (35), 107 (30), 91 (20), 77 (10), 65 (15). RMS (ESI): m/z calcd for C , found S10

11 -{[4-chloro-2,6-diphenyl)phenyl]methyl}-4-methylaniline 6d Cl Light yellow solid, yield = 86%, 1 MR (200 Mz, CDCl 3 ): δ = (m, 12), 6.84 (d, 2, J = 8.2 z), 6.11 (d, 2, J = 8.2 z), 4.14 (s, 2), 3.35 (s, 1), 2.19 (s, 3). 13 C MR (50 Mz, CDCl 3 ): δ = , , 140.3, 132.9, 132.5, 129.4, 129.3, 128.9, 128.4, 127.7, 126.7, 113.3, 43.1, GC: t R = 32.3 min. MS (EI): m/z: 385 (25, M + ), 383 (65, M + ), 277 (45), 242 (100), 226 (10), 165 (10), 120 (15), 91 (15), 77 (10), 65 (10). RMS (ESI): m/z calcd for C Cl , found ; m/z calcd for C , found {[4-chloro-2,6-di(4- tolyl))phenyl]methyl}-4-methylaniline (6e) Cl Yellow solid, yield = 71%, 1 MR (300 Mz, CDCl 3 ): δ = (m, 10), 6.85 (d, 2, J = 8.4 z), 6.15 (d, 2, J = 8.4 z), 4.15 (s, 2), 3.35 (brs, 1), 2.43 (s, 6), 2.21 (s, 3). 13 C MR (75 Mz, CDCl 3 ): δ = 145.1, 145.0, 137.5, 134.4, 133.0, 132.4, 129.4, 129.2, 128.8, 127.6, 126.6, 113.4, 43.2, 21.2, GC: t R = 36.8 min. MS (EI): m/z (relative intensity) 413 (20, M + ), 411 (60, M + ), 307 (17), 305 (50), 270 (100), 255 (35), 239 (15), 120 (15), 107 (20), 91(15), 65 (10). RMS (ESI): m/z calcd for C Cla , found {[4-methyl-2,6-diphenyl)phenyl]methyl}-4-methylaniline (6f) White solid, yield = 72%, 1 MR (300 Mz, CDCl 3 ): δ = (m, 12), 6.84 (d, 2, J = 8.1 z), 6.15 (d, 2, J = 8.1 z), 4.15 (s, 2), 3.37 (brs, 1), 2.43 (s, 3), 2.20 (s, 3). 13 C MR (75 Mz, CDCl 3 ): δ = 145.4, 143.3, 141.7, 136.7, 131.2, 130.5, 129.3, 129.1, 128.3, 127.2, 126.4, 113.3, 43.3, 21.0, GC: t R = 24.9 min. MS (EI): m/z (relative intensity) 364 (20, M + + ), 363 (60, M + ), 257 (100), 242 (40), 179 (15), 91(30), 77 (10). RMS (ESI): m/z calcd for C , found {[4-methyl-2,6-di(4- tolyl))phenyl]methyl}-4-methylaniline (6g) 3 C Light yellow oil, yield = 54%, 1 MR (300 Mz, CDCl 3 ): δ = 7.37 (d, 4, J = 8.1 z),7.26 (m, 6), 6.85 (d, 2, J = 8.1 z), 6.17 (d, 2, J = 8.1 z), 4.14 (s, 2), 3.45 (brs, 1), 2.42 (s, 6), 2.41 (s, 3), 2.20 (s, 3). 13 C MR (75 Mz, CDCl 3 ): δ = 145.5, 143.2, 138.8, 136.8, 136.6, 131.3, 130.4, 129.6, 129.3, 129.0, 126.2, 113.3, 43.3, 21.2, 21.0, GC: t R = 34.2 min. MS (EI): m/z (relative intensity) 392 (15, M + ), 391 (50), 388 (15), 285 (100), 270 (30), 255 (25), 91(10). RMS (ESI): m/z calcd for C a , found S11

12 -{[4-methyl-2,6-di(4-fluorophenyl))phenyl]methyl}-4-methylaniline (6h) 3 C Orange solid, yield = 82%, 1 MR (300 Mz, CDCl 3 ): δ = (m, 4), (m, 6), 6.88 (d, 2, J = 8.1 z), 6.20 (d, 2, J = 8.1 z), 4.05 (s, 2), 3.32 (brs, 1), 2.43 (s, 3), 2.22 (s, 3). 13 C MR (75 Mz, CDCl 3 ): δ = (d, J C = 245 z), 145.2, 142.4, (d, 2, J = 3.5 z), 137.0, 131.3, (d, 2, J = 4.0 z), 130.6, 129.5, 126.8, (d, 2, J = 21.2 z), 113.2, 43.4, 21.0, MR (188 Mz, CDCl 3 ): δ = GC: t R = 23.4 min. MS (EI): m/z (relative intensity) 399 (70), 294 (20), 293 (100), 278 (35), 258 (15), 183 (10), 120 (10), 109 (20), 91 (15), 77 (10). RMS (ESI): m/z calcd for C , found J.. artley, M. D. Phillips, T. D. James, ew J. Chem. 2002, 26, P. Purushottamachar, A. Khandelwal, T. S. Vasaitis, R. D. Bruno, L. K. Gediya, V. C. O. jar, Bioorg. Med. Chem. 2008, 16, aka, D. Koseki, Y. Kondo Adv. Synth. Catal. 2008, 350, W. Li, G. ou, M. Chang, X. Zhang, Adv. Synth. Catal. 2009, 351, S. Oi, Y. Ogino S. ukita, Y. Inoue, Org. Lett. 2002, 4, S12