Steering Amide Synthesis from Acetonitrile by Electrochemically Derived Active Superoxide
Abstract
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 K 2 CO 3 electrolyte containing methanol, we achieved over 94% selectivity toward acetamide at a total current density up to 104 mA cm −2 , with a productivity of 878 µmol cm −2 h −1 . 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.
Article Details
Authors (7)
Ling‐Yu Dong
State Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials Liaoning Key Laboratory for Catalytic Conversion of Carbon Resources and School of Chemical Engineering Dalian University of Technology Dalian 116024 P.R. China
Yu‐Tai Wu
State Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials Liaoning Key Laboratory for Catalytic Conversion of Carbon Resources and School of Chemical Engineering Dalian University of Technology Dalian 116024 P.R. China
Yi‐Fan Wang
State Key Laboratory of Medicinal Chemical Biology Tianjin Key Laboratory of Biosensing and Molecular Recognition Frontiers Science Centre For New Organic Matter Research Centre for Analytical Sciences College of Chemistry School of Medicine and Frontiers Science Center for Cell Responses Nankai University Tianjin P.R. China
Min‐Yi Zhu
State Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials Liaoning Key Laboratory for Catalytic Conversion of Carbon Resources and School of Chemical Engineering Dalian University of Technology Dalian 116024 P.R. China
Honglei Wang
University of Strasbourg, CNRS, ISIS UMR 7006, 8 Allée Gaspard Monge, Strasbourg F-67000, France
Guang‐Ping Hao
State Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials Liaoning Key Laboratory for Catalytic Conversion of Carbon Resources and School of Chemical Engineering Dalian University of Technology Dalian 116024 P.R. China
An‐Hui Lu
State Key Laboratory of Fine Chemicals Frontier Science Center for Smart Materials Liaoning Key Laboratory for Catalytic Conversion of Carbon Resources and School of Chemical Engineering Dalian University of Technology Dalian 116024 P.R. China