Fang Wei, Meng Yan-Dong, Ding Shu-Ying, Wang Ju-Yan, Pei Zheng-Hao, Shen Meng-Lan, Yao Chuan-Zhi, Li Qiankun, Gu Zhenhua, Yu Jie, Jiang Hua-Jie
Department of Applied Chemistry, Anhui Province Engineering Laboratory for Green Pesticide Development and Application, and Anhui Province Key Laboratory of Crop Integrated Pest Management, Anhui Agricultural University, Hefei, 230036, China.
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui, 230026, China.
Angew Chem Int Ed Engl. 2025 Feb 10;64(7):e202419596. doi: 10.1002/anie.202419596. Epub 2024 Dec 11.
An efficient enantioselective coupling reaction between sulfenamides and cyclic diaryliodonium salts is established via adaptive Cu/anionic stereogenic-at-Co(III) complex combined catalysis, precisely synthesizing a broad range of axially chiral sulfilimines with excellent enantioselectivities, diastereoselectivities, regioselectivities, and chemoselectivities (67 examples under same conditions, up to 98 % ee). The following thermodynamically controlled pyramidal inversion enables efficient stereodivegent synthesis of all four stereoisomers. Mechanistic studies suggest that anionic stereogenic-at-cobalt(III) complexes serve as counteranions of diaryliodonium and anionic ligand of Cu(I) catalyst simultaneously, which could be regarded as an explanation for outstanding selectivities.
通过适应性铜/钴（III）中心手性阴离子配合物联合催化，实现了亚磺酰胺与环状二芳基碘鎓盐之间高效的对映选择性偶联反应，精确合成了一系列具有优异对映选择性、非对映选择性、区域选择性和化学选择性的轴手性亚砜亚胺（相同条件下67例，高达98% ee）。随后的热力学控制的锥形翻转实现了所有四种立体异构体的高效立体发散合成。机理研究表明，钴（III）中心手性阴离子配合物同时作为二芳基碘鎓盐的抗衡阴离子和铜（I）催化剂的阴离子配体，这可以解释其出色的选择性。
