Electrocatalysis as an enabling technology for organic synthesis.

Electrochemistry has recently gained increased attention as a versatile strategy for achieving challenging transformations at the forefront of synthetic organic chemistry. Electrochemistry’s unique ability to generate highly reactive radical and radical ion intermediates in a controlled fashion under mild conditions has inspired the development of a number of new electrochemical methodologies for the preparation of valuable chemical motifs. Particularly, recent developments in electrosynthesis have featured an increased use of redox-active electrocatalysts to further enhance control over the selective formation and downstream reactivity of these reactive intermediates. Furthermore, electrocatalytic mediators enable synthetic transformations to proceed in a manner that is mechanistically distinct from purely chemical methods, allowing for the subversion of kinetic and thermodynamic obstacles encountered in conventional organic synthesis. This review highlights key innovations within the past decade in the area of synthetic electrocatalysis, with emphasis on the mechanisms and catalyst design principles underpinning these advancements. A host of oxidative and reductive electrocatalytic methodologies are discussed and are grouped according to the classification of the synthetic transformation and the nature of the electrocatalyst.

电化学作为一种通用策略，最近在合成有机化学前沿实现具有挑战性的转化方面受到了越来越多的关注。电化学在温和条件下以可控方式产生高活性自由基和自由基离子中间体的独特能力，激发了许多用于制备有价值化学结构的新型电化学方法的开发。特别是，电合成的近期发展特点是越来越多地使用氧化还原活性电催化剂，以进一步加强对这些活性中间体的选择性形成和后续反应性的控制。此外，电催化介质使合成转化能够以一种在机理上不同于纯化学方法的方式进行，从而能够克服常规有机合成中遇到的动力学和热力学障碍。本综述重点介绍了过去十年合成电催化领域的关键创新，强调了支撑这些进步的机制和催化剂设计原理。讨论了一系列氧化和还原电催化方法，并根据合成转化的分类和电催化剂的性质进行了分组。