Copper-Catalyzed Three-Component Sulfur-Stereogenic Sulfilimination of Conjugated and Cumulated Dienes

Transition-metal and organocatalyzed two-electron processes have enabled enantioselective sulfilimination. However, the radical-mediated asymmetric variant remains a significant challenge, especially in a multicomponent manner. Herein, we unveil a copper-catalyzed three-component enantioselective allylsulfilimination of sulfenamides with diversely functionalized delayed allyl radicals generated via radical addition to conjugated or cumulated dienes. Building on a radical relay strategy, this synthetic platform accommodates a plethora of destabilized aryl and fluoroalkyl radicals as well as mono- and disubstituted dienes, enabling the modular assembly of functionalized di-, tri-, and tetra-substituted homoallylic sulfilimines featuring a sulfur-stereogenic center with high enantioselectivity. The utility is exemplified by late-stage allylsulfilimination of sugar, natural products, and pharmaceutical derivatives, allowing rapid access to various analogues with enhanced structural diversity.