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Herein, we disclose a straightforward, robust, and simple route to access β‐substituted desaturated cyclic amines via an electrochemically driven desaturative β‐functionalization of cyclic amines. This transformation is based on multiple single‐electron oxidation processes using catalytic amounts of ferrocene. The reaction proceeds in the absence of stoichiometric amounts of electrolyte under mild conditions, affording the desired products with high chemo‐ and regioselectivity. The reaction was tolerant of a broad range of substrates and also enables late‐stage β‐C(sp3)−H acylation of potentially valuable products. Preliminary mechanistic studies using cyclic voltammetry reveal the key role of ferrocene as a redox mediator in the reaction. [ABSTRACT FROM AUTHOR]

Electrochemistry. An electrochemical desaturative α‐acylation of cyclic N‐aryl amines to access α‐substituted enamines is reported in the Communication by Youai Qiu et al. (e202115178). [ABSTRACT FROM AUTHOR]