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TEMPO-Enabled Electrochemical Enantioselective Oxidative Coupling of Secondary Acyclic Amines with Ketones
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2021-09-17 , DOI: 10.1021/jacs.1c08671
Zhen-Hua Wang 1 , Pei-Sen Gao 1 , Xiu Wang 1 , Jun-Qing Gao 2 , Xue-Tao Xu 2 , Zeng He 1 , Cong Ma 1 , Tian-Sheng Mei 1
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An electrochemical asymmetric coupling of secondary acyclic amines with ketones via a Shono-type oxidation has been described, affording the corresponding amino acid derivatives with good to excellent diastereoselectivity and enantioselectivity. The addition of an N-oxyl radical as a redox mediator could selectively oxidize the substrate rather than the product, although their oxidation potential difference is subtle (about 13 mV). This electrochemical transformation proceeds in the absence of stoichiometric additives, including metals, oxidants, and electrolytes, which gives it good functional group compatibility. Mechanistic studies suggest that proton-mediated racemization of the product is prevented by the reduction of protons at the cathode.

中文翻译:

TEMPO 使能的无环仲胺与酮的电化学对映选择性氧化偶联

已经描述了仲无环胺与酮通过 Shono 型氧化的电化学不对称偶联,提供了具有良好至优异的非对映选择性和对映选择性的相应氨基酸衍生物。添加N-氧基自由基作为氧化还原介质可以选择性氧化底物而不是产物,尽管它们的氧化电位差异很小(约 13 mV)。这种电化学转化在没有化学计量添加剂(包括金属、氧化剂和电解质)的情况下进行,这使其具有良好的官能团兼容性。机理研究表明,质子介导的产物外消旋化可通过阴极处质子的还原来防止。
更新日期:2021-09-29
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