Site-selective α-C(sp3)-H amination and etherification of amides via copper-photoredox catalysis.

Aryl radical-mediated intramolecular 1,5-hydrogen atom transfer (1,5-HAT) represents a powerful strategy for the remote selective functionalization of inert C-H bonds. Herein, we report a photoinduced copper-catalyzed α-C(sp3)-H N/O-functionalization of amides enabled by aryl radical-mediated 1,5-HAT. This strategy provides an efficient and straightforward access to install aza-heterocycles and phenols onto aliphatic amine scaffolds, exhibiting broad functional group tolerance (48 examples), high efficiency (up to 95% yield), and excellent regioselectivity with exclusive α-functionalization.