Regio‐, Stereo‐, and Enantioselective Copper‐Catalyzed Allylation of Sulfinylamines with Allenes

Abstract Sulfinamides, pivotal scaffolds in modern organic synthesis, have undergone a continuous evolution of synthetic methodologies over the past century, yet the precise construction of sulfur stereocenters remains a significant synthetic challenge. Herein, we report a versatile catalytic asymmetric strategy for the synthesis of S‐chirogenic allyl sulfinamides through the direct allylation of sulfinylamines with allenes. Our methodology employs a catalytic system comprising copper salts, hydrosilanes, and readily accessible chiral ligands, which facilitates the in situ generation of organocopper surrogates via hydrocupration of allenes. This approach demonstrates remarkable substrate scope and excellent regio‐, stereo‐, and enantioselectivity across a diverse array of sulfinamide products. Comprehensive mechanistic investigations, including detailed experimental studies and computational analyses, have been conducted to elucidate the reaction pathway and identify the key factors governing enantioselectivity.