Native Amine-Directed NiH-Catalyzed Markovnikov Hydroalkynylation of Unactivated Alkenes.

The native amine-directed hydroalkynylation of unactivated alkenes remains a significant challenge because of the strong coordination ability of free amines and the difficulty in controlling regioselectivity during alkene functionalization. Herein, we report a NiH-catalyzed Markovnikov-selective hydroalkynylation of unactivated alkenes enabled by a diamine-based ligand. This operationally simple protocol provides efficient access to structurally diverse β-, γ- and δ-aminoalkynes from readily available alkenyl amines and alkynyl bromides under mild conditions. The practicality of this method is further demonstrated through gram-scale synthesis and late-stage functionalization of pharmaceutically relevant molecules.