TEMPO-Enabled Electrochemical Enantioselective Oxidative Coupling of Secondary Acyclic Amines with Ketones

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...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2021-09, Vol.143 (38), p.15599-15605
Main Authors: Wang, Zhen-Hua, Gao, Pei-Sen, Wang, Xiu, Gao, Jun-Qing, Xu, Xue-Tao, He, Zeng, Ma, Cong, Mei, Tian-Sheng
Format: Article
Language:English
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Summary: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.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.1c08671