Copper‐Catalyzed Enantioselective C(sp3)−SCF3 Coupling of Carbon‐Centered Benzyl Radicals with (Me4N)SCF3

Abstract In contrast with the well‐established C(sp 2 )−SCF 3 cross‐coupling to forge the Ar−SCF 3 bond, the corresponding enantioselective coupling of readily available alkyl electrophiles to forge chiral C(sp 3 )−SCF 3 bond has remained largely unexplored. We herein disclose a copper‐catalyzed enantioselective radical C(sp 3 )−SCF 3 coupling of a range of secondary/tertiary benzyl radicals with the easily available (Me 4 N)SCF 3 reagent. The key to the success lies in the utilization of chiral phosphino‐oxazoline‐derived anionic N,N,P‐ligands through tuning electronic and steric effects for the simultaneous control of the reaction initiation and enantioselectivity. This strategy can successfully realize two types of asymmetric radical reactions, including enantioconvergent C(sp 3 )−SCF 3 cross‐coupling of racemic benzyl halides and three‐component 1,2‐carbotrifluoromethylthiolation of arylated alkenes under mild reaction conditions. It therefore provides a highly flexible platform for the rapid assembly of an array of enantioenriched SCF 3 ‐containing molecules of interest in organic synthesis and medicinal chemistry.