Adaptive Photochemical Amination via Co(II) Catalysis.

Transition-metal-catalyzed amination of aryl halides is one of the most employed methods for constructing -arylation adducts. However, the broad success of these reactions largely relies on the screening of precatalysts, elaborated ligands, and case-by-case optimization of reaction conditions (solvent, base, additive, temperature, ) for electronically or structurally diverse nucleophiles. Herein, we report an adaptive photochemical C-N coupling of aryl halides with various nitrogen nucleophiles (aliphatic and aromatic amines, amides, sulfonamides, pyrazoles, and ammonium salts) by Co(II) catalysis under the same reaction conditions (same precatalyst, same ligand, same base, same solvent, same temperature) without the addition of any exogenous photocatalyst. This photochemical amination features a wide substrate scope (>130 examples, up to 95% yield) with excellent functional group tolerance. Mechanistic studies indicate that these C-N coupling reactions may proceed via a Co(I)/Co(III) catalytic cycle.