Organocatalytic Dynamic Kinetic Resolution for the Stereoconvergent Synthesis of N–N Axially Chiral Compounds

Dynamic kinetic resolution (DKR) serves as a fundamental approach in asymmetric synthesis which enables the efficient conversion of racemic starting materials into a single stereoisomer, yet its extension to racemic diastereomers remains a formidable challenge, and reported DKR processes have largely been restricted to substrates bearing a single stereogenic element. Herein, we report an organocatalytic DKR with catalyst‐accelerated racemization and epimerization for the asymmetric construction of significant N–N axially chiral compounds through the merger of a reversible Pudovik addition with an irreversible, stereoselective phospha ‐Brook rearrangement. Under bioinspired peptide‐phosphonium salt catalysis, a wide range of N–N axially chiral products were obtained in good yields and high enantioselectivities. Scale‐up synthesis and product derivatization further underscore the synthetic utility of this protocol. Mechanistic studies support a DKR process involving reversible racemization and epimerization through prochiral intermediates, identify the phospha ‐Brook rearrangement as the stereodetermining step, and reveal key roles of hydrogen‐bonding and ion‐pairing interactions in catalyst‐controlled stereochemical induction. This work establishes a new paradigm for the catalytic asymmetric synthesis of axially chiral molecules.