Enol/Enamine-Mediated Asymmetric Synthesis Beyond Central Chirality

The catalytic asymmetric construction of complex, enantioenriched molecules remains a fundamental aspect of contemporary synthetic chemistry. Enols and enamines, by virtue of their ambident nucleophilicity and planar prochiral α-carbon, function as exceptionally versatile intermediates in asymmetric synthesis. In light of the growing interest in stereochemical frameworks beyond central chirality, enol and enamine chemistry has been expanded to facilitate the synthesis of molecules with axial, inherent, helical, and mechanically planar chirality. This review surveys the remarkable progress made over the past decade in this field. It encompasses a variety of activation modes-including chiral amines, N-heterocyclic carbenes (NHCs), chiral phosphoric acids (CPAs), phase-transfer catalysts, and metal complexes-that enable precise stereocontrol. Structured according to catalytic systems, this review provides a critical and systematic analysis of emerging strategies, highlights current trends, and addresses the ongoing challenges within this rapidly evolving field.