Deaminative C(sp3)-C(sp2) and C(sp3)-S coupling of alkylamines.

Herein, we describe a radical-mediated directly deaminative functionalization strategy for primary alkylamines using commercially available O-diphenylphosphoryl hydroxylamine (DPPH) as the deaminating reagent. By employing sulfonyl oxime ethers, thiosulfonates, and phenylsulfonyl benzothiazoles as effective radical acceptors, a series of deaminative C(sp3)-C(sp2) and C(sp3)-S coupling reactions of amines have been successfully realized. These transformations proceed via in situ formation of isodiazene intermediates followed by the generation of alkyl carbon-centered radicals, thereby enabling efficient construction of C(sp3)-C(sp2) and C(sp3)-S bonds. The protocol features mild reaction conditions, good functional group tolerance, and simple operation.