Catalytic Methylene Insertion between Amines and Terminal Alkynes via C–N Bond Cleavage of N,N‑Dimethylacetamide: A Unique Route to Propargylic Amines

A copper-based system allows for the methylene insertion between an amine and a milder nucleophile, including a terminal alkyne counterpart, via C–N bond cleavage of N,N-dimethylacetamide. The method gives an expedient access to propargylic amines in good to excellent yields. A wide-ranging substrate scope and late-stage functionalization of complex molecules make the protocol practically valuable.