Transition-Metal-Assisted Radical/Radical Cross-Coupling: A New Strategy to the Oxidative C(sp3)–H/N–H Cross-Coupling

A transition-metal-assisted oxidative C(sp3)-H/N–H cross-coupling reaction of N-alkoxyamides with aliphatic hydrocarbons is described. During the reaction, nitrogen radicals were generated from the oxidation of N-alkoxyamides. Experiments and DFT calculations revealed that transition-metal catalyst could lower the reactivity of the generated nitrogen radical by the coordination of the transition metal, which allowed the selective radical/radical cross-coupling with the transient sp3 carbon radical to construct C(sp3)–-N bonds. Various C(sp3)–H bonds could be transformed into C(sp3)–N bonds through this radical amidation strategy.