Zou Xi, Wang Xinghua, Duan Zhaowang, Jiao Hongjian, Lan Yu, Su Xinhui, Gao Bing
Institute of Drug Discovery and Design, College of Pharmaceutical Sciences, Zhejiang University, Hangzhou, Zhejiang, China.
State Key Laboratory of Chemo and Biosensing, College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, China.
Nat Commun. 2025 Jul 8;16(1):6277. doi: 10.1038/s41467-025-61429-2.
Kinetic resolution is a promising strategy for accessing enantioenriched molecules from racemic mixtures. However, this method has not previously been realized in the synthesis of chiral sulfinyl scaffolds via S(IV)-X bond exchange. We disclose a kinetic resolution reaction of sulfinamides with alcohols in this report. It affords sulfinate esters and enantioenriched sulfinamides with high enantioselectivity across a broad substrate scope. These two products serve as versatile chiral sulfinyl reagents, enabling further transformation into diverse functional molecules. Mechanistic studies suggest a dual activation transition state, wherein both the sulfinamide and alcohol substrates are engaged by a squaramide catalyst through hydrogen-bonding interactions. This method offers a mechanistic and synthetic complement to established dynamic asymmetric processes for constructing chiral sulfinyl frameworks.
动力学拆分是一种从外消旋混合物中获得对映体富集分子的有前景的策略。然而，这种方法此前尚未在通过S(IV)-X键交换合成手性亚砜基骨架中得以实现。我们在本报告中披露了一种磺酰胺与醇的动力学拆分反应。它能在广泛的底物范围内以高对映选择性提供亚磺酸酯和对映体富集的磺酰胺。这两种产物可作为通用的手性亚砜基试剂，能够进一步转化为各种功能分子。机理研究表明存在一种双重活化过渡态，其中磺酰胺和醇底物均通过氢键相互作用与方酰胺催化剂结合。该方法为构建手性亚砜基骨架的既定动态不对称过程提供了一种机理和合成上的补充。
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