Regioreversed Carbosulfenylation of Fluoroalkenes via Nickel‐Mediated Radical Sorting

Abstract Carbosulfenylation of olefins represents an important class of reactions for the synthesis of structurally diverse organosulfur compounds. Previous studies typically yield 1,2‐regioselectivity. In the context of diversity‐oriented synthesis, accessing the regioreversed products is desirable, significantly broadening the scope of these reactions. In this study, we report a nickel‐catalyzed 2,1‐carbosulfenylation of trifluoromethyl‐ and gem ‐difluoroalkenes, using free thiols and benzyl bromides as sulfur and carbon sources, respectively. The unusual regioselectivity observed is enabled by a “radical sorting” mechanism. The Ni catalyst activates benzyl bromide to generate a benzylic radical that undergoes hydrogen atom transfer (HAT) with the thiol to form a sulfur‐centered radical. The sulfur radical subsequently adds to the fluoroalkenes, resulting in an α‐fluoroalkyl C‐radical. This radical undergoes S H 2 with a Ni–CH 2 Ar to form a C(sp 3 )─C(sp 3 ) bond and quaternary center, ultimately producing valuable fluoroalkyl thioethers. Isotopic labeling experiments corroborate a hydrogen atom transfer (HAT) event within the working mechanism.