3-chloro-N,N-dimethylaniline

Conditions: temp:120.01; pressure:0.00; stir:

Procedure: Prepared from 3-chloro-N,N-dimethylaniline (1h, 31.0 mg, 0.200 mmol, 1.00 equiv) and catBH (36.0 mg, 0.300 mmol, 1.50 equiv) according to GP 1. The title compound was purified by flash column chromatography using cyclohexane/EtOAc/Et3N (30/1/1) as eluent to afford 3h (37.1 mg, 66%) as a white solid.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: This reaction is carried out in the same manner as the reaction in example 3. The difference is that, the reactants are 3-(N,N-Dimethylamino)phenyl chloride (156.0 mg, 0.99 mmol), palladium cinnamyl chloride (7.8 mg, 0.015 mmol), 2-Methoxy-6-(N-methyl-N-phenyl-amino)henyldicyclohexyl)phosphine (24.6 mg, 0.060 mmol), Cs2CO3 (653.2 mg, 2.0 mmol) in 4.0 mL acetone at 90° C. for 12 h. 1-[3′-(N, N-Dimethylamino)phenyl]-2-propanone (122.2 mg) was obtained with a yield of 69% as liquid. 1H NMR (300 MHz, CDCl3) δ 7.21 (t, J=7.8 Hz, 1H, ArH), 6.69-6.62 (m, 1H, ArH), 6.61-6.53 (m, 2H, ArH), 3.64 (s, 2H, CH2), 2.95 (s, 6H, N(CH3)2), 2.15 (s, 3H, COCH3); 13C NMR (75 MHz, CDCl3) δ 207.0, 150.7, 135.0, 129.3, 117.4, 113.1, 111.1, 51.6, 40.4, 28.9; IR (neat) v (cm−1) 3033, 2916, 2805, 1712, 1603, 1580, 1504, 1440, 1354, 1271, 1229, 1178, 1156, 1062; MS (70 eV, EI) m/z (%): 178 (M++1, 9.69), 177 (M+, 73.88), 134 (100). This reaction is carried out in the same manner as the reaction in example 3 at 90° C. for 12 h

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: This reaction is carried out in the same manner as the reaction in example 3. The difference is that, the reactants are 3-(N,N-Dimethylamino)phenyl chloride (156.0 mg, 0.99 mmol), palladium cinnamyl chloride (7.8 mg, 0.015 mmol), 2-Methoxy-6-(N-methyl-N-phenyl-amino)henyldicyclohexyl)phosphine (24.6 mg, 0.060 mmol), Cs2CO3 (653.2 mg, 2.0 mmol) in 4.0 mL acetone at 90° C. for 12 h. 1-[3′-(N, N-Dimethylamino)phenyl]-2-propanone (122.2 mg) was obtained with a yield of 69% as liquid. 1H NMR (300 MHz, CDCl3) δ 7.21 (t, J=7.8 Hz, 1H, ArH), 6.69-6.62 (m, 1H, ArH), 6.61-6.53 (m, 2H, ArH), 3.64 (s, 2H, CH2), 2.95 (s, 6H, N(CH3)2), 2.15 (s, 3H, COCH3); 13C NMR (75 MHz, CDCl3) δ 207.0, 150.7, 135.0, 129.3, 117.4, 113.1, 111.1, 51.6, 40.4, 28.9; IR (neat) v (cm−1) 3033, 2916, 2805, 1712, 1603, 1580, 1504, 1440, 1354, 1271, 1229, 1178, 1156, 1062; MS (70 eV, EI) m/z (%): 178 (M++1, 9.69), 177 (M+, 73.88), 134 (100). This reaction is carried out in the same manner as the reaction in example 3 at 90° C. for 12 h

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: This reaction is carried out in the same manner as the reaction in example 3. The difference is that, the reactants are 3-chloro-N,N-dimethylaniline (155.9 mg, 1.0 mmol), propiophenone (160.9 mg, 1.2 mmol), palladium acetate (6.7 mg, 0.030 mmol), 2-Methoxy-6-(N-methyl-N-phenyl-amino)phenyl(dicyclohexyl)phosphine (18.4 mg, 0.045 mmol), t-BuONa (116.1 mg, 1.2 mmol) in 3 mL dry toluene at 110° C. for 11.5 h. 2-[3′-(N, N-dimethylamino)phenyl]-1-phenyl-1-propanone (200.7 mg) was obtained with a yield of 79% as liquid. 1H NMR (300 MHz, CDCl3) δ 8.03-7.97 (m, 2H, ArH), 7.52-7.44 (m, 1H, ArH), 7.43-7.35 (m, 2H, ArH), 7.20-7.11 (m, 1H, ArH), 6.65-6.55 (m, 3H, ArH), 4.19 (s, 2H, CH2), 2.87 (s, 6H, 2×CH3); 13C NMR (75 MHz, CDCl3) δ 197.7, 150.6, 136.4, 135.1, 132.8, 129.1, 128.5, 128.4, 117.4, 113.1, 110.9, 45.9, 40.3; IR (neat) v (cm−1) 3056, 2891, 2804, 1679, 1601, 1579, 1501, 1447, 1354, 1330, 1276, 1205, 1180, 1155, 1062; MS (70 eV, EI) m/z (%): 240 (M++1, 10.27), 239 (M+, 54.99), 105 (100); HRMS calcd for C16H17NO (M+): 239.1310. Found: 239.1309. This reaction is carried out in the same manner as the reaction in example 3 at 110° C. for 11.5 h

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: This reaction is carried out in the same manner as the reaction in example 3. The difference is that, the reactants are 3-chloro-N,N-dimethylaniline (155.9 mg, 1.0 mmol), propiophenone (160.9 mg, 1.2 mmol), palladium acetate (6.7 mg, 0.030 mmol), 2-Methoxy-6-(N-methyl-N-phenyl-amino)phenyl(dicyclohexyl)phosphine (18.4 mg, 0.045 mmol), t-BuONa (116.1 mg, 1.2 mmol) in 3 mL dry toluene at 110° C. for 11.5 h. 2-[3′-(N, N-dimethylamino)phenyl]-1-phenyl-1-propanone (200.7 mg) was obtained with a yield of 79% as liquid. 1H NMR (300 MHz, CDCl3) δ 8.03-7.97 (m, 2H, ArH), 7.52-7.44 (m, 1H, ArH), 7.43-7.35 (m, 2H, ArH), 7.20-7.11 (m, 1H, ArH), 6.65-6.55 (m, 3H, ArH), 4.19 (s, 2H, CH2), 2.87 (s, 6H, 2×CH3); 13C NMR (75 MHz, CDCl3) δ 197.7, 150.6, 136.4, 135.1, 132.8, 129.1, 128.5, 128.4, 117.4, 113.1, 110.9, 45.9, 40.3; IR (neat) v (cm−1) 3056, 2891, 2804, 1679, 1601, 1579, 1501, 1447, 1354, 1330, 1276, 1205, 1180, 1155, 1062; MS (70 eV, EI) m/z (%): 240 (M++1, 10.27), 239 (M+, 54.99), 105 (100); HRMS calcd for C16H17NO (M+): 239.1310. Found: 239.1309. This reaction is carried out in the same manner as the reaction in example 3 at 110° C. for 11.5 h

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using a THF solution of phenylmagnesium bromide (1.19 mL, 1.01 M, 1.2 mmol) and 3-chloro-N,N-dimethylaniline (155.6 mg, 1.0 mmol) as starting materials, the reaction was performed at a scale of 1.0 mmol at 60° C. for 24 hours in the same manner as in Example 2. After performing silica gel column chromatography (toluene=50 and 100% in hexane), the above compound was obtained as a colorless liquid (0.185 g, yield=94%, purity=>98% (GC analysis)). the above compound was obtained as a colorless liquid (0.185 g, yield=94%, purity=>98% (GC analysis))

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: This reaction is carried out in the same manner as the reaction in example 3. The difference is that, the reactants are 3-(N,N-Dimethylamino)phenyl chloride (156.0 mg, 0.99 mmol), palladium cinnamyl chloride (7.8 mg, 0.015 mmol), 2-Methoxy-6-(N-methyl-N-phenyl-amino)henyldicyclohexyl)phosphine (24.6 mg, 0.060 mmol), Cs2CO3 (653.2 mg, 2.0 mmol) in 4.0 mL acetone at 90° C. for 12 h. 1-[3′-(N, N-Dimethylamino)phenyl]-2-propanone (122.2 mg) was obtained with a yield of 69% as liquid. 1H NMR (300 MHz, CDCl3) δ 7.21 (t, J=7.8 Hz, 1H, ArH), 6.69-6.62 (m, 1H, ArH), 6.61-6.53 (m, 2H, ArH), 3.64 (s, 2H, CH2), 2.95 (s, 6H, N(CH3)2), 2.15 (s, 3H, COCH3); 13C NMR (75 MHz, CDCl3) δ 207.0, 150.7, 135.0, 129.3, 117.4, 113.1, 111.1, 51.6, 40.4, 28.9; IR (neat) v (cm−1) 3033, 2916, 2805, 1712, 1603, 1580, 1504, 1440, 1354, 1271, 1229, 1178, 1156, 1062; MS (70 eV, EI) m/z (%): 178 (M++1, 9.69), 177 (M+, 73.88), 134 (100). This reaction is carried out in the same manner as the reaction in example 3 at 90° C. for 12 h

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: This reaction is carried out in the same manner as the reaction in example 3. The difference is that, the reactants are 3-chloro-N,N-dimethylaniline (155.9 mg, 1.0 mmol), propiophenone (160.9 mg, 1.2 mmol), palladium acetate (6.7 mg, 0.030 mmol), 2-Methoxy-6-(N-methyl-N-phenyl-amino)phenyl(dicyclohexyl)phosphine (18.4 mg, 0.045 mmol), t-BuONa (116.1 mg, 1.2 mmol) in 3 mL dry toluene at 110° C. for 11.5 h. 2-[3′-(N, N-dimethylamino)phenyl]-1-phenyl-1-propanone (200.7 mg) was obtained with a yield of 79% as liquid. 1H NMR (300 MHz, CDCl3) δ 8.03-7.97 (m, 2H, ArH), 7.52-7.44 (m, 1H, ArH), 7.43-7.35 (m, 2H, ArH), 7.20-7.11 (m, 1H, ArH), 6.65-6.55 (m, 3H, ArH), 4.19 (s, 2H, CH2), 2.87 (s, 6H, 2×CH3); 13C NMR (75 MHz, CDCl3) δ 197.7, 150.6, 136.4, 135.1, 132.8, 129.1, 128.5, 128.4, 117.4, 113.1, 110.9, 45.9, 40.3; IR (neat) v (cm−1) 3056, 2891, 2804, 1679, 1601, 1579, 1501, 1447, 1354, 1330, 1276, 1205, 1180, 1155, 1062; MS (70 eV, EI) m/z (%): 240 (M++1, 10.27), 239 (M+, 54.99), 105 (100); HRMS calcd for C16H17NO (M+): 239.1310. Found: 239.1309. This reaction is carried out in the same manner as the reaction in example 3 at 110° C. for 11.5 h