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Despite widespread use of the deuterium isotope effect, selective deuterium labeling of chemical molecules remains a major challenge. Herein, a facile and general electrochemically driven, organic mediator enabled deuteration of styrenes with deuterium oxide (D2O) as the economical deuterium source was reported. Importantly, this transformation could be suitable for various electron rich styrenes mediated by triphenylphosphine (TPP). The reaction proceeded under mild conditions without transition‐metal catalysts, affording the desired products in good yields with excellent D‐incorporation (D‐inc, up to >99 %). Mechanistic investigations by means of isotope labeling experiments and cyclic voltammetry tests provided sufficient support for this transformation. Notably, this method proved to be a powerful tool for late‐stage deuteration of biorelevant compounds. [ABSTRACT FROM AUTHOR]

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]

Herein, an electrochemically driven NiH‐catalyzed reductive coupling of alkyl halides and alkyl alkenes for the construction of Csp3−Csp3 bonds is firstly reported. Notably, alkyl halides serve dual function as coupling substrates and as hydrogen sources to generate NiH species under electrochemical conditions. The tunable nature of this reaction is realized by introducing an intramolecular coordinating group to the substrate, where the product can be easily adjusted to give the desired branched products. The method proceeds under mild conditions, exhibits a broad substrate scope, and affords moderate to excellent yields with over 70 examples, including late‐stage modification of natural products and drug derivatives. Mechanistic insights offer evidence for an electrochemically driven coupling process. The sp3‐carbon‐halogen bonds can be activated through single electron transfer (SET) by the nickel catalyst in its low valence state, generated by cathodic reduction, and the generation of NiH species from alkyl halides is pivotal to this transformation. [ABSTRACT FROM AUTHOR]

Elektrochemie. Die elektrochemische desaturierende α‐Acylierung von cyclischen N‐Arylaminen zu α‐substituierten Enaminen wird in der Zuschrift von Youai Qiu et al. vorgestellt (e202115178). [ABSTRACT FROM AUTHOR]

-Acylation, Desaturation, Electrochemistry, Ferrocene mediator, Selectivity Keywords: -Acylation; Desaturation; Electrochemistry; Ferrocene mediator; Selectivity EN -Acylation Desaturation Electrochemistry Ferrocene mediator Selectivity 1 1 1 01/28/22 20220201 NES 220201 B Elektrochemie b . Frontispiz: Electrochemical Desaturative -Acylation of Cyclic N-Aryl Amines. [Extracted from the article]