Ni(II)‐Catalyzed 1,2‐Alkynylhydroxylation of Mono‐, Di‐, Tri‐ and Tetrasubstituted Alkenes: Diastereo‐ and Regio‐selective Synthesis of Homopropargylic Alcohols

Abstract Few methods have been reported for the alkynylhydroxylation of unactivated alkenes, which could synchronously introduce both alkyne and hydroxyl groups into alkene moieties to construct homopropargylic alcohol scaffolds. Herein, we explored an unprecedented Ni(II)‐catalyzed selective Heck‐type 1,2‐alkynylhydroxylation of unactivated alkenes with alkynylsilanes under air. The β, γ‐ and γ, δ‐unsaturated amides, including mono‐, di‐, tri‐ and tetrasubstituted alkenyl amides, were reactive substrates to afford a powerful platform for preparing important homopropargylic alcohols with excellent regio‐ and diastereo‐selectivity. This method was suitable for use in late‐stage modification of complex molecules.