近日，大连理工大学郝广平团队实现了电化学衍生活性超氧化物催化乙腈合成酰胺。这一研究成果发表在2025年9月11日出版的《德国应用化学》杂志上。

酰胺具有独特的羰基-氮键，是广泛的天然和合成产品、药品、农用化学品和关键中间体的活性和必需的基本官能团。酰胺键的形成是化学中最基本的反应之一。传统的酰胺合成方法面临原子经济性差和依赖有害试剂的挑战。

研究组提出了一种串联电热催化途径，利用电化学产生的超氧自由基在环境条件下引导氧插入，从乙腈合成乙酰胺。超氧自由基是通过控制分子氧的电还原形成的。在1 M含甲醇的K₂CO₃电解质中，研究组对乙酰胺的选择性超过94%，总电流密度高达104 mA cm^-2、产率为878 μmol cm^-2 h^-1。

机理研究表明，缓冲碱性环境稳定的超氧自由基促进了腈基上的亲核C─O偶联，而甲醇的存在则淬灭了羟基自由基，有效抑制了乙酰胺过度氧化成乙酸酯。这种耦合的电热催化可以合成多种酰胺，并可能通过活性氧介导的过程激发更复杂的有机合成。

附：英文原文

Title: Steering Amide Synthesis from Acetonitrile by Electrochemically Derived Active Superoxide

Author: Ling-Yu Dong, Yu-Tai Wu, Yi-Fan Wang, Min-Yi Zhu, Honglei Wang, Guang-Ping Hao, An-Hui Lu

Issue&Volume: 2025-09-11

Abstract: Amides with unique carbonyl-nitrogen linkage are fundamental functional groups that are active and essential for a wide range of natural and synthetic products, pharmaceuticals, agrochemicals, and key intermediates. Amide bond formation is one of the most fundamental reactions in chemistry. Conventional amide synthesis faces challenges of poor atom economy and reliance on hazardous reagents. Herein, we present a tandem electro-thermal catalytic pathway for the synthesis of acetamide from acetonitrile, leveraging electrochemically generated superoxide radicals to steer oxygen insertion under ambient conditions. The superoxide radicals were formed via controlled electroreduction of molecular oxygen. In 1 M K2CO3 electrolyte containing methanol, we achieved over 94% selectivity toward acetamide at a total current density up to 104 mA cm2, with a productivity of 878 μmol cm2 h1. Mechanistic studies reveal that the superoxide radicals stabilized by a buffered alkaline environment facilitated the nucleophilic C─O coupling at the nitrile group, while the presence of methanol quenched the hydroxyl radicals and effectively suppressed the over-oxidation of acetamide to acetate. This coupled electro-thermal catalysis enables the synthesis of a large variety of amides and may inspire more complex organic synthesis through active oxygen species-mediated process.

DOI: 10.1002/anie.202513359

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202513359