Access to Axially Chiral Vinyl Sulfilimines via Copper‐Catalyzed Enantioselective Radical Relay Trifluoromethyl‐Sulfilimination of Terminal Alkynes

Abstract Sulfilimines have garnered increasing attention as valuable scaffolds in drug discovery and asymmetric synthesis. Nevertheless, catalytic enantioselective construction of sulfilimines in both axial and point chirality chemical space remains a substantial challenge. Herein, we report copper‐catalyzed atroposelective sulfilimination of terminal alkynes with sulfenamides via a radical relay mechanism, enabling the direct assembly of axially chiral vinyl sulfilimines with high levels of chemo‐, regio‐, diastereo‐, and enantioselectivity. The success of this strategy hinges on the atroposelective trapping of transient high active vinyl radicals by a chiral Cu–sulfinimidoyl intermediate. Experimental and computational mechanistic studies reveal a novel asymmetric radical sulfilimination mechanism through an enantioselective reductive elimination of a Cu(III) intermediate, thereby establishing a mechanism distinct from outer‐sphere HAT‐initiated radical–radical coupling or S H 2 pathway.