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钴催化的亚磺酰胺的催化对映选择性还原芳基化和烯基化反应以制备亚磺酰胺

Catalytic Enantioselective Reductive Arylation and Alkenylation of Sulfinylamines to Access Sulfinamides Enabled by Cobalt Catalysis.

作者信息

Yuan Yin, Tian Xinyu, Zheng Hongxia, Li Yuze, Zhang Junliang, Yang Junfeng

机构信息

Department of Chemistry, Fudan University, 2205 Songhu Road, Shanghai, 200438, China.

Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou, 450001, China.

出版信息

Angew Chem Int Ed Engl. 2025 Jun 24;64(26):e202506243. doi: 10.1002/anie.202506243. Epub 2025 May 8.

Abstract

This study reports a cobalt-catalyzed method for the enantioselective reductive arylation and alkenylation of sulfinylamines, facilitating the efficient synthesis of enantiopure sulfinamides. By employing a cobalt/chiral diphosphine and tridentate ligand system, a range of diverse aryl and alkenyl iodides were successfully transformed into sulfinamides, achieving high yields and excellent enantioselectivity. This methodology underscores the utility of sulfinylamines as versatile electrophilic sulfur sources. Detailed mechanistic insights from density functional theory (DFT) calculations suggest that the key step involves migratory insertion into the sulfilimine group, which plays a crucial role in enantioselectivity. These findings offer a sustainable approach for the development of biologically relative enantiopure sulfur-containing compounds.

摘要

本研究报道了一种钴催化的亚磺酰胺对映选择性还原芳基化和烯基化方法,有助于高效合成对映体纯的亚磺酰胺。通过采用钴/手性二膦和三齿配体体系,一系列不同的芳基和烯基碘化物成功转化为亚磺酰胺,实现了高产率和优异的对映选择性。该方法强调了亚磺酰胺作为通用亲电硫源的实用性。密度泛函理论(DFT)计算得出的详细机理见解表明,关键步骤涉及迁移插入亚磺亚胺基团,这在对映选择性中起关键作用。这些发现为开发具有生物学相关性的对映体纯含硫化合物提供了一种可持续的方法。

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