Regiodivergent Hydroaminoalkylation of Alkynes and Allenes by a Combined Rhodium and Photoredox Catalytic System.

A rhodium/photoredox dual catalyzed regiodivergent α-allylation of amines is described. As an atom-economic and efficient method, alkynes and allenes are used as allylic electrophile surrogates in this novel protocol. With different reaction conditions, synthetically useful branched or linear homoallylic amines could be synthesized in good to excellent yields and regioselectivity. This straightforward strategy complements the traditional transition-metal catalyzed allylation reactions.