Enantioselective C–H Functionalization Reactions Enabled by Cobalt(III)‐Centered Chiral Pockets

Due to the difficulty in achieving stereoselective recognition of three-dimensional functionalization reagents, desymmetrization and (dynamic) kinetic resolution of such complex architectures via transition-metal-catalyzed asymmetric C─H functionalization remains highly challenging. Herein, we develop a novel platform for enantioselective C─H functionalization enabled by trivalent-cobalt-centered chiral pockets. It achieves two formidable tasks in stereochemical control: (1) the desymmetrization of prochiral biaryls to access enantioenriched axially chiral molecules, and (2) the kinetic resolution of racemic [2.2]paracyclophanes to construct planar-chiral architectures. Integrated mechanistic and computational studies allowed us to unravel the intricate details of how the cobalt(III)-centered chiral pockets achieve precise, substrate-specific recognition within congested 3D molecular frameworks.