2-N-(2-chlorophenyl)-2-N-methylbenzene-1,2-diamine

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

Procedure: Compound 3 (0.842 g, 3.62 mmol), o-iodonitrobenzene (1.35 g, 5.43 mmol), Pd2(dba)3 (0.104 g, 5% mol), BINAP (0.170 g, 7.5%), Cs2CO3 (2.35 g, 7.42 mmol) and 12 mL of toluene were placed in a pressure tube. The mixture was purged with argon at room temperature for 15 min. The tube was sealed and placed in an oil bath at 80-90° C. for 30 h. When thin-layer chromatography (TLC) showed consumption of compound 3, the reaction mixture was filtered through silica gel with a 90:10 mixture of ethyl acetate:dichloromethane. The solvent was then removed under vacuum. The product was purified by column chromatography on silica gel using a 8:92 mixture of methyl chloride:petroleum ether as the eluent to afford the product as a red crystalline solid (0.785 g, 80% yield). 1H NMR (300 MHz, CDCl3) δ 9.03 (1H, bs), 8.07 (1H, dd, J=8.7, 1.5 Hz), 7.32-7.19 (4H, m), 7.12-6.99 (5H, m), 6.90 (1H, ddd, J=8.0, 6.9, 2.2 Hz), 6.68 (1H, ddd, J=8.4, 6.9, 1.2 Hz), 3.16 (3H, s); 13C (75 MHz, CDCl3) δ 147.2 (q), 145.1 (q), 142.4 (q), 135.2 (t), 131.6 (q), 130.7 (t), 129.5 (q), 127.4 (t), 126.5 (t), 126.5 (t), 126.0 (t), 124.8 (t), 124.0 (t), 123.2 (t), 121.7 (t), 117.0 (t), 115.8 (t), 40.6. The mixture was purged with argon at room temperature for 15 min The tube was sealed consumption of compound 3 the reaction mixture was filtered through silica gel with a 90:10 mixture of ethyl acetate The solvent was then removed under vacuum The product was purified by column chromatography on silica gel using a 8:92 mixture of methyl chloride

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

Procedure: Compound 2 (0.121 g, 0.46 mmol) was stirred at room temperature in MeOH (4.6 mL). To this, CuCl (0.137 g, 1.38 mmol) was added and mixture stirred at room temperature for 5-10 min. KBH4 (0.174 g, 3.22 mmol) was added in portions. The reaction was stirred at room temperature until the solution became clear. The reaction was quenched with deionized H2O and extracted 3 times with 15 mL of a 90:10 mixture of ethyl acetate:dichloromethane. The organic layers were combined and dried over Na2SO4. The solvent was removed to give a brownish-black solid (107 mg, 100% yield). 1H NMR (300 MHz, CDCl3) δ 7.32 (1H, dd, J=7.8, 1.4 Hz), 7.25 (1H, dd, J=7.3, 1.7 Hz), 7.22 (1H, dd, J=7.1, 1.7 Hz), 7.16, (1H, dd, J=8.0, 1.6 Hz), 7.00-6.95 (2H, m), 6.76 (1H, ddd, J=9.3, 7.7, 1.4 Hz), 6.67 (1H, ddd, J=8.9, 7.6, 1.5 Hz); 13C (75 MHz, CDCl3) δ 147.6 (q), 142.2 (q), 136.9 (q), 130.7 (t), 130.68 (q), 127.4 (t), 125.5 (t), 123.6 (t), 121.9 (t), 118.6 (t), 115.8 (t), 41.1. The reaction was stirred at room temperature until the solution The reaction was quenched with deionized H2O extracted 3 times with 15 mL of a 90:10 mixture of ethyl acetate dried over Na2SO4 The solvent was removed