Photoinduced Arene C‐H Amination with Ammonia: A Practical and Regioselective Strategy for Primary Amines

Introducing the primary amino group into aromatic ring is one of the most important study issues in organic chemistry, particularly for the pharmaceuticals and agrochemicals chemistry. Herein, we describe a photoinduced direct C−H amination of arenes with ammonia via the site‐selective C−H thianthrenation that forms a new C−N bond with excellent regioselectivity. The reaction is carried out under mild conditions, and with a wide range of functional group tolerance, such as sensitive −Cl, −Br, and −OH groups which are poorly tolerated in conventional approaches. Moreover, the synthetic utility of our amination protocol has been confirmed through late‐stage modification and gram‐scale synthesis of complex drug‐like molecules.