Aminocatalysis is a well‐established tool that enables the production of enantioenriched compounds under mild conditions. Its versatility is underscored by its seamless integration with various synthetic approaches. While the combination of aminocatalysis with metal catalysis, photochemistry, and stoichiometric oxidants has been extensively explored, its synergy with electrochemical activation remains largely unexplored. Herein, we present the successful merger of electrochemistry and aminocatalysis to perform SOMO‐type transformations, expanding the toolkit for asymmetric electrochemical synthesis. The methodology harnesses electricity to drive the oxidation of catalytically generated enamines, which ultimately partake in enantioselective radical processes, leading to α‐alkylated aldehydes. Crucially, mechanistic studies highlight how this electrochemical strategy is enabled by the use of a redox shuttle, 4,4’‐dimethoxybiphenyl, to prevent catalyst degradation and furnishing the coveted compounds in good yield and high enantioselectivity.

中文翻译：

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氧化还原梭实现醛的电化学不对称自由基官能化

氨基催化是一种成熟的工具，可以在温和条件下生产富含对映体的化合物。其与各种合成方法的无缝集成凸显了其多功能性。虽然氨基催化与金属催化、光化学和化学计量氧化剂的组合已被广泛探索，但其与电化学活化的协同作用仍然很大程度上未被探索。在此，我们展示了电化学和氨基催化的成功合并，以进行 SOMO 型转化，扩展了不对称电化学合成的工具包。该方法利用电力驱动催化生成的烯胺的氧化，最终参与对映选择性自由基过程，产生α-烷基化醛。至关重要的是，机理研究强调了如何通过使用氧化还原梭（4,4'-二甲氧基联苯）来实现这种电化学策略，以防止催化剂降解并以良好的产率和高对映选择性提供令人垂涎的化合物。