Nickel‐Catalyzed Asymmetric Hydrophosphinamidation of Alkynes

ABSTRACT P ‐stereogenic phosphinamidates are highly pivotal structural motifs in drug discovery and the design of chiral ligands. Despite their utility, catalytic enantioselective access to these compounds remains a formidable challenge. Herein, we report the first nickel‐catalyzed asymmetric hydrophosphinamidation of alkynes. This protocol enables the highly efficient and enantioselective synthesis of structurally diverse alkenyl phosphinamidates, accommodating a wide array of both N, N ‐dialkyl and N ‐alkyl substituted H ‐phosphinamides. Notably, the resulting products exhibit orthogonal reactivities at four distinct sites, serving as a powerful and universal platform for the divergent synthesis of complex P ‐stereogenic architectures.