A General Platform for S-Stereogenic α-Fluoroalkyl S(IV/VI) Compounds via Enantioselective Radical Fluoroalkylation of Sulfenamides.

α-Fluoroalkyl-substituted high-valent sulfur motifs are important structural elements in fluorinated molecule design and exhibit broad application potential in diverse fields. However, access to S-stereogenic α-fluoroalkyl S(IV/VI) compounds still relies largely on classical resolution, resulting in limited efficiency and selectivity. We herein report a copper-catalyzed asymmetric radical C-S cross-coupling that effectively tames highly reactive α-fluoroalkyl radicals, enabled by a sequential stereodiscrimination-chirality transfer strategy, providing rapid access to S-chiral α-fluoroalkyl sulfilimines. Integrated with downstream transformations, this reaction serves as a general and systematic platform for S-chiral α-fluoroalkyl S(IV/VI) compounds. The synthetic utility of the method is demonstrated by gram-scale synthesis and concise access to diverse chiral fluoroalkyl reagents and bioisosteres of sulfur-containing drugs.