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

Abstract

An organocatalytic dynamic kinetic resolution merges reversible Pudovik addition with stereoselective phospha-Brook rearrangement, converting racemic diastereomers into N–N axially chiral compounds. Bioinspired peptide-phosphonium salt catalysis enables catalyst-accelerated racemization and epimerization, affording good yields and high enantioselectivities. Mechanistic studies identify the rearrangement as stereodetermining and reveal synergistic hydrogen-bonding/ion-pairing control over asymmetric induction, establishing a new paradigm for axially chiral molecule synthesis.