Chiral phosphoric acids (CPAs) have emerged as highly effective Brønsted acid catalysts in an expanding range of asymmetric transformations, often through novel multifunctional substrate activation modes. Versatile and broadly appealing, these catalysts benefit from modular and tunable structures, and compatibility with additives. Given the unique types of noncovalent interactions (NCIs) that can be established between CPAs and various reactants─such as hydrogen bonding, aromatic interactions, and van der Waals forces─it is unsurprising that these catalyst systems have become a promising approach for accessing diverse chiral product outcomes. This review aims to provide an in-depth exploration of the mechanisms by which CPAs impart stereoselectivity, positioning NCIs as the central feature that connects a broad spectrum of catalytic reactions. Spanning literature from 2004 to 2024, it covers nucleophilic additions, radical transformations, and atroposelective bond formations, highlighting the applicability of CPA organocatalysis. Special emphasis is placed on the structural and mechanistic features that govern CPA-substrate interactions, as well as the tools and techniques developed to enhance our understanding of their catalytic behavior. In addition to emphasizing mechanistic details and stereocontrolling elements in individual reactions, we have carefully structured this review to provide a natural progression from these specifics to a broader, class-level perspective. Overall, these findings underscore the critical role of NCIs in CPA catalysis and their significant contributions to advancing asymmetric synthesis.
