Kinetics‐Based Approach to Developing Electrocatalytic Variants of Slow Oxidations: Application to Hydride Abstraction‐Initiated Cyclization Reactions
Kinetics‐Based Approach to Developing Electrocatalytic Variants of Slow Oxidations: Application to Hydride Abstraction‐Initiated Cyclization Reactions
复制标题
基于动力学的方法开发缓慢氧化的电催化变体：应用于氢化物提取引发的环化反应
DOI：
10.1002/chem.202200335
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Floreancig, Paul E.
中科院分区：
文献类型：
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作者：
Lawrence, Jean‐Marc I. A.;Floreancig, Paul E.
电化学氧化剂再生在具有缓慢氧化还原步骤的反应中具有挑战性，因为还原氧化剂的稳态浓度低，导致难以维持足够的电流或防止电位尖峰。这项工作表明，应用对中间阳离子稳定性，氧化剂强度，过电位和反应动力学浓度之间关系的理解，提供了一种在氢化物提取引发的环化反应中进行电化学氧代铵离子再生的方法，从而开发出具有高氧化过渡态自由能的过程的电催化变体。这种方法应适用于扩大电催化的范围，包括额外的缓慢氧化还原过程。
Electrochemical oxidant regeneration is challenging in reactions that have a slow redox step because the steady‐state concentration of the reduced oxidant is low, causing difficulties in maintaining sufficient current or preventing potential spikes. This work shows that applying an understanding of the relationship between intermediate cation stability, oxidant strength, overpotential, and concentration on reaction kinetics delivers a method for electrochemical oxoammonium ion regeneration in hydride abstraction‐initiated cyclization reactions, resulting in the development of an electrocatalytic variant of a process that has a high oxidation transition state free energy. This approach should be applicable to expanding the scope of electrocatalysis to include additional slow redox processes.