Kinetics-Based Approach to Developing Electrocatalytic Variants of Slow Oxidations: Application to Hydride Abstraction-Initiated Cyclization Reactions.

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.