Visible‐Light‐Driven Copper(II)‐Catalyzed Direct C–H Amination of Arenes via N‐Centered Radicals

The catalytic formation of C(sp 2 )N bonds through direct C–H functionalization remains a crucial method in the synthesis of aromatic amines. Herein, we report an efficient visible‐light‐driven, copper‐catalyzed direct C–H amination of arenes employing stable N‐amino pyridinium salts as versatile N ‐centered radical precursors. The mild photocatalytic system generated from Cu(OAc) 2 and the 6,6′‐dimethyl‐2,2′‐bipyridine ligand enables efficient CN bond formation under mild conditions and exhibits broad functional group compatibility across a diverse range of arenes. Mechanistic investigations, including UV–visible absorption and electron paramagnetic resonance studies, reveal the photoinduced generation of Cu(I) species from the [Cu(dmbpy)(OAc) 2 ] complex via visible‐light‐induced homolysis. Moreover, successful late‐stage functionalization underscores the versatility of this visible‐light‐driven copper‐catalytic platform, enabling efficient access to aminated pharmaceutical analogs.