Cobalt/Salox‐Catalyzed Enantioselective C−H Functionalization of Arylphosphinamides

Abstract Previous methods on Co III ‐catalyzed asymmetric C−H activation rely on the use of tailor‐made cyclopentadienyl‐ligated Co III complexes, which require lengthy steps for the preparation. Herein, we report an unprecedented enantioselective C−H functionalization enabled by a simple cobalt/salicyloxazoline (Salox) catalysis. The chiral Salox ligands can be easily prepared in one step from salicylonitrile and chiral amino alcohols. A broad range of P‐stereogenic compounds were synthesized in high yields with excellent enantioselectivities (45 examples, up to 99 % yield and >99 % ee). The isolation and characterization of several intermediates provided insights into the generation of active catalytic cobalt species, the action of Salox, and the mode of stereocontrol.