近日，美国康奈尔大学Lin, Song团队研究了手性支撑电解质对磷化氢的动态动力学拆分。2025年7月16日出版的《自然》杂志发表了这项成果。

由于手性中心在生物体系中的普遍存在以及同手性对分子性质的影响，对映不纯化合物的合成一直是有机化学的研究热点。随着人们越来越认识到电化学是提高有机合成范围和可持续性的有力工具，人们越来越多地致力于开发不对称电催化反应来获得具有挑战性的手性分子。

然而，许多主题电化学反应依赖于没有催化剂的直接电解，这使得它们本质上难以呈现对映选择性。辅助电解质是电化学系统不可或缺的组成部分，除了确保足够的溶液导电性外，它们还能影响电化学转化的速率和选择性。手性支持电解质可通过直接电解介导不对称反应，但其在有机电合成中的主题仍未被广泛探索。

研究组描述了亚化学计量手性磷酸盐作为支持电解质的主题，以促进外消旋三价磷化氢氧化产生对映体富集的磷化氢氧化物。他们的方法依赖于动态动力学解析策略，该策略利用阳极生成的磷酰自由基阳离子的快速金字塔型转化，而在电极-电解质界面处高浓度的手性磷酸盐增强了限速亲核加成过程中的对映选择性控制。该结果突出了手性支持电解质促进自由基离子介导的不对称转化的前景。

附：英文原文

Title: Dynamic kinetic resolution of phosphines with chiral supporting electrolytes

Author: Mao, Kaining, Liu, Chenfei, Wang, Yi, Gu, Chaoxuan, Putziger, John M., Cemalovic, Nicholas I., Muniz, Cameron, Qi, Yue, Lin, Song

Issue&Volume: 2025-07-16

Abstract: The synthesis of enantiopure compounds is a central focus in organic chemistry owing to the prevalence of chiral centres in biological systems and the impact of homochirality on molecular properties. With growing recognition of electrochemistry as a powerful tool to improve the scope and sustainability of organic synthesis1, increasing efforts have been directed towards developing asymmetric electrocatalytic reactions to access challenging chiral molecules2,3,4. However, many useful electrochemical reactions rely on direct electrolysis without a catalyst, making them inherently difficult to render enantioselective. Supporting electrolytes are integral to electrochemical systems and, in addition to ensuring sufficient solution conductivity, they can influence the rate and selectivity of electrochemical transformations5. Chiral supporting electrolytes can mediate asymmetric reactions via direct electrolysis, but their use in organic electrosynthesis remains largely unexplored6,7. Here we describe the use of substoichiometric chiral phosphate salts as supporting electrolytes to facilitate the oxidation of racemic trivalent phosphines to afford enantioenriched phosphine oxides. Our approach relies on a dynamic-kinetic-resolution strategy that exploits the rapid pyramidal inversion of an anodically generated phosphoniumyl radical cation8, while a high concentration of chiral phosphate at the electrode–electrolyte interface9,10 enhances enantioselective control during rate-limiting nucleophilic addition. Our results highlight the promise of chiral supporting electrolytes for promoting radical-ion-mediated asymmetric transformations.

DOI: 10.1038/s41586-025-09238-x

Source: https://www.nature.com/articles/s41586-025-09238-x