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

2021; American Chemical Society; Volume: 143; Issue: 38 Linguagem: Inglês

10.1021/jacs.1c08671

1943-2984

Zhenhua Wang, Pei‐Sen Gao, Xiu Wang, Jun-Qing Gao, Xue-Tao Xu, Zeng He, Cong Ma, Tian‐Sheng Mei,

Oxidative Organic Chemistry Reactions

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.