N‑Directed, Radical Relay Enantioconvergent\nSulfinylation of Distal C(sp<sup>3</sup>)–H Bonds via Cobalt\nCatalysis

Cobalt-catalyzed\nenantioconvergent cross-coupling of C(sp<sup>3</sup>)–H bonds\nwith <i>in situ</i>-generated sulfenate\nanions is achieved to access chiral sulfoxides, which are found in\nthe structures of many biologically active agents. The more challenging\naliphatic C–H bonds as well as sterically hindered substrates\ncontaining tertiary C–H bonds could also be tolerated well.\nMechanistic studies indicate that the transformation could undergo\na Co<sup>II</sup>S(O)R-mediated single-electron transfer with <i>N</i>-fluorocarboxamides, followed by a 1,5-hydrogen atom transfer\nand then a pivotal organocobalt(IV)-controlled enantioselective cross-coupling\nprocess. This novel asymmetric radical reaction for C–S bond\nconstruction could open a new door for the synthesis of sulfur-centered\nchiral compounds.