Controlling Stereoselectivity with Noncovalent Interactions in Chiral Phosphoric Acid Organocatalysis,Chemical Reviews

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Controlling Stereoselectivity with Noncovalent Interactions in Chiral Phosphoric Acid Organocatalysis
Chemical Reviews ( IF 51.4 ) Pub Date : 2025-03-18 , DOI: 10.1021/acs.chemrev.4c00869
Isaiah O Betinol ₁ , Yutao Kuang ₁ , Brian P Mulley ₁ , Jolene P Reid ₁

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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.

中文翻译：

在手性磷酸有机催化中用非共价相互作用控制立体选择性

手性磷酸（CPA）已成为高效的 Brønsted 酸催化剂，通常通过新型多功能底物活化模式，在不断扩大的不对称转化范围内出现。这些催化剂用途广泛，具有广泛的吸引力，受益于模块化和可调结构以及与添加剂的兼容性。鉴于 CPA 和各种反应物（例如氢键、芳香族相互作用和范德华力）之间可以建立独特类型的非共价相互作用（NCI），这些催化剂系统已成为获得不同手性产物结果的有前途的方法也就不足为奇了。本综述旨在深入探索 CPA 赋予立体选择性的机制，将 NCIs 定位为连接广泛催化反应的中心特征。它跨越 2004 年至 2024 年的文献，涵盖了亲核加成、自由基转化和无选择性键形成，突出了 CPA 有机催化的适用性。特别强调控制 CPA-底物相互作用的结构和机理特征，以及为增强我们对 CPA 催化行为的理解而开发的工具和技术。除了强调单个反应中的机理细节和立体控制元素外，我们还精心构建了这篇综述，以提供从这些细节到更广泛的类级视角的自然进展。总体而言，这些发现强调了 NCI 在 CPA 催化中的关键作用及其对推进不对称合成的重大贡献。

更新日期：2025-03-19

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