近日，重庆大学李存璞团队报道了电极“鸡尾酒效应”实现乙腈的电荷选择性C-C键断裂用于芳基卤化物甲基化。相关论文于2026年4月8日发表在《德国应用化学》杂志上。

在芳香骨架上引入单个甲基可深刻改变分子的性质与生物活性。然而，由于难以在不使用有机金属催化剂的情况下选择性断裂C-C键并稳定生成的甲基物种，利用简单廉价的乙腈实现可控的芳香甲基化仍具挑战性。

研究组报道了一种由不锈钢阴极实现的电极控制电化学甲基化策略，其中，电荷差异化的Cr、Fe和Ni位点通过协同相互作用产生的多金属“鸡尾酒效应”，促进了乙腈的极化、选择性C-C键断裂以及表面吸附甲基自由基的稳定化。采用芴作为单电子转移介体，选择性活化芳基卤化物并生成芳基自由基，随后该自由基进攻电极表面稳定的甲基自由基，得到甲基化产物。这种电极-介体协同体系能够实现多种性质底物的选择性偶联，为可控自由基转化提供了一个通用平台。

附：英文原文

Title: Electrode “Cocktail Effect” Enables Charge Selective C─C Bond Cleavage of Acetonitrile for Aryl Halide Methylation

Author: Baijing Wu, Hongliang Fan, Shujie Li, Donghui Gao, Meiqi Geng, Minhua Shao, Cunpu Li, Zidong Wei

Issue&Volume: 2026-04-08

Abstract: The introduction of a single methyl group onto aromatic frameworks can profoundly alter molecular properties and biological activity. However, controllable aromatic methylation using simple and inexpensive acetonitrile remains challenging due to the difficulty of selectively cleaving the C─C bond and stabilizing the resulting methyl species without organometallic catalysts. Herein, we report an electrode-controlled electrochemical methylation strategy enabled by a stainless steel cathode, in which a multi-metallic “cocktail effect” arising from the cooperative interaction of charge-differentiated Cr, Fe, and Ni sites promotes acetonitrile polarization, selective C─C bond cleavage, and stabilization of surface-adsorbed methyl radicals. Fluorene is employed as a single electron transfer mediator to selectively activate aryl halides and generate aryl radicals, which subsequently attack the electrode-stabilized methyl radicals to afford the methylated products. This cooperative electrode-mediator system enables selective coupling of substrates with diverse properties and provides a general platform for controlled radical transformations.

DOI: 10.1002/anie.5830573

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.5830573