[Br:1][C:2]1[CH:13]=[CH:12][C:5]2[NH:6][CH2:7][CH2:8][N:9]([CH3:11])[CH2:10][C:4]=2[CH:3]=1.[Cl:14][C:15]1[CH:20]=[CH:19][C:18](I)=[CH:17][CH:16]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Br:1][C:2]1[CH:13]=[CH:12][C:5]2[N:6]([C:18]3[CH:19]=[CH:20][C:15]([Cl:14])=[CH:16][CH:17]=3)[CH2:7][CH2:8][N:9]([CH3:11])[CH2:10][C:4]=2[CH:3]=1
A mixture of 7-bromo-4-methyl-2,3,4,5-tetrahydro-1H-benzo[e][1,4]diazepine (2.25 g, 9.33 mmol), 1-chloro-4-iodobenzene (3.10 g, 12.1 mmol), 2-(dicyclohexylphosphino)-2′,4′,6′-tri-i-isopropyl-1,1′-biphenyl (444 mg, 0.933 mmol), and cesium carbonate (6.1 g, 18.7 mmol) in toluene (60 mL) was purged with argon for 10 minutes before palladium(II) acetate (210 mg, 0.993 mmol) was added. After purging with argon for 5 minutes, the reaction mixture was heated at reflux overnight. The mixture was cooled, partitioned with water (100 mL) and ethyl acetate (3×50 mL). The combined organic extracts were dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by flash chromatography eluting with 10:1 methylene chloride/methanol followed by rechromatography eluting with 3:1 methylene chloride/ethyl acetate to yield 7-bromo-1-(4-chlorophenyl)-4-methyl-2,3,4,5-tetrahydro-1H-benzo[e][1,4]diazepine (694 mg, 21%) as a brown foam: 1H NMR (CDCl3, 500 MHz) δ 7.45 (s, 1H), 7.37 (d, J=8.4 Hz, 1H), 7.12 (d, J=6.8 Hz, 2H), 7.01 (d, J=8.4 Hz, 1H), 6.62 (d, J=6.9 Hz, 2H), 3.71-3.67 (m, 2H), 3.60 (s, 2H), 2.88-2.85 (m, 2H), 2.36 (s, 3H); ESI MS m/z 351, 353 [M+H]+.
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