Copper‐Catalyzed Radical Enantioselective Carbo‐Esterification of Styrenes Enabled by a Perfluoroalkylated‐PyBox Ligand

Abstract Chiral lactones are found in many natural products. The reaction of simple alkenes with iodoacetic acid is a powerful method to build lactones, but the enantioselective version of this reaction has not been implemented to date. Herein, we report the efficient catalytic radical enantioselective carbo‐esterification of styrenes enabled by a newly developed Cu I ‐perfluoroalkylated PyBox system. Simple styrenes have been converted to useful chiral lactones, whose synthetic applications are showcased. Mechanistic studies reveal that this reaction is a rare example of an efficient ligand‐decelerated system, in which the ligand decelerates the reaction, but the reaction is still efficient with reduced amounts of ligand. This uncommon catalytic system may inspire further consideration of the effect of ligands in asymmetric catalysis.