Enantio- and Diastereoselective Reductive Propargylic Sulfinamidation Enabled by Synergistic Bimetallic Catalysis

In this manuscript, we present a groundbreaking strategy for the efficient synthesis of S-propargyl sulfinamides, featuring both stereogenic sulfur(IV) centers and alkyne motifs, through the asymmetric addition of racemic propargyl acetates to sulfinylamines. Our innovative approach leverages a synergistic nickel/copper dual-catalytic system, wherein each metal center is coordinated by a distinct chiral ligand. This system demonstrates unparalleled control over chiral sulfur centers, accommodating both primary and tertiary propargylic acetates. Notably, reactions involving secondary propargylic acetates achieve exceptional enantio- and diastereoselectivity for both the carbon and sulfur stereocenters. Comprehensive mechanistic studies reveal the distinct and complementary roles of nickel and copper catalysis in facilitating this high degree of stereoselective control, offering new insights into the design of complex catalytic systems for asymmetric synthesis.