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.