Nickel-Metallaphotoredox-Catalyzed Radical Cross-Couplings to Access α-Aryl-α-trifluoromethyl Amines Under Flow Conditions.

Herein, we report a method for the synthesis of α-aryl-α-trifluoromethyl amines via dual photoredox/nickel-catalysis between aryl bromides and N-trifluoroethyl hydroxylamine under flow conditions. This protocol enables the first direct 1-aminotrifluoroethylation of benzene derivatives under mild conditions in high yields (up to 84%) and with a wide functional group tolerance (32 examples). The transformation proceeds through photoinduced single-electron reduction of N-trifluoroethyl hydroxylamine, followed by 1,2-hydrogen atom transfer, to generate the α-aminotrifluoroethyl radical for cross-coupling of aryl bromides.