Adaptive Photochemical Amination via Co(II) Catalysis

Transition-metal-catalyzed amination of aryl halides is one of the most employed methods for constructing N-arylation ad-ducts. However, the broad success of these reactions is largely relying on the screening of pre-catalysts, elaborating ligands, and case-by-case optimization of the reaction conditions (solvent, base, additive, temperature etc.) and electronic or struc-tural diversities of nucleophiles, for forging diverse C-N coupling products. Herein, we reported an adaptive photochemical C-N coupling of aryl halides with various nitrogen nucleophiles (aliphatic and aromatic amines, amides, sulfonamides, pyra-zoles, and ammonium salts) by Co(II) catalysis under the same reaction conditions (same pre-catalyst, 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 this C-N coupling reactions may proceed via a Co(I)/Co(III) catalytic cycle.