Aminoalkyl radicals as halogen-atom transfer agents for activation of alkyl and aryl halides

Organic halides are important building blocks in synthesis but their use in (photo)redox chemistry is limited by their low reduction potentials. Halogen-atom transfer still remains the most reliable approach to exploit these substrates in radical processes despite its requirement for hazardous reagents and initiators such as tributyltin hydride. Herein, we demonstrate that aaminoalkyl radicals, easily accessible from simple amines, promote the homolytic activation of 15
carbon–halogen bonds with a reactivity profile mirroring that of classical tin radicals. This strategy conveniently engages alkyl and aryl halides in a wide range of redox transformations to construct sp3–sp3, sp3–sp2 and sp2–sp2 carbon–carbon bonds under mild conditions with high chemoselectivity.