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.

中文翻译：

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次磺酰胺的不对称 S-芳基化反应可获得由阴离子立体产生钴 （III） 配合物实现的轴向手性硫胺


通过自适应 Cu/阴离子立体生成 Co（III） 复合物联合催化，建立了次磺酰胺和环状二芳基二烯铵盐之间的高效对映选择性偶联反应，精确合成了多种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向手性巯嘧啶（相同条件下有 67 个例子，高达 98% ee）。以下热力学控制的锥体倒置可实现所有四种立体异构体的高效立体分离合成。机理研究表明，阴离子立体生钴 （III） 配合物同时充当二芳基铵的对阴离子和 Cu（I） 催化剂的阴离子配体，这可以被视为对出色选择性的解释。