Teaching Old Compounds New Tricks: DDQ‐Photocatalyzed C−H Amination of Arenes with Carbamates, Urea, and N‐Heterocycles

The C−H amination of benzene derivatives was achieved using DDQ as photocatalyst and BocNH(2) as the amine source under aerobic conditions and visible light irradiation. Electron‐deficient and electron‐rich benzenes react as substrates with moderate to good product yields. The amine scope of the reaction comprises Boc‐amine, carbamates, pyrazoles, sulfonimides and urea. Preliminary mechanistic investigations indicate arene oxidation by the triplet of DDQ to radical cations with different electrophilicity and a charge transfer complex between the amine and DDQ as intermediate of the reaction.