Regioselective 1,2-Hydrogen Atom Transfer of N-Centered Radicals for C(sp ³ )–C(sp ³ ) Coupling to Generate 1,2-Diamine Derivatives

Herein, 2-azaallyl anions are reported as super electron donors (SEDs) in the reduction of <i>N</i>-chlorodialkylamines to generate N-centered radicals (NCRs). The NCRs undergo regioselective net 1,2-hydrogen atom transfer (1,2-HAT) to yield C-centered radicals, which subsequently participate in C(sp³)-C(sp³) intermolecular radical cross-coupling with 2-azaallyl radicals, culminating in the generation of 1,2-diamine derivatives (30 examples, up to 85% yield). A telescoped gram-scale synthesis and hydrolysis of the product demonstrated the synthetic potential of this method. Mechanistic investigations, including radical trapping, radical clock experiments, and density functional theory calculations, provide significant evidence for an intramolecular radical net 1,2-HAT pathway.