The mechanism of Shono oxidation is studied by combining cyclic voltammetry, a computational ferrocene reference electrode, and density functional theory. The study identified the role of proton-coupled electron transfer in the oxidation pathway. The approach allows for the calculation of both electron and proton transfer, as well as their coupled transfer steps, such that preferred reaction pathways can be identified.

Electrochemical processes are of particular interest in modern chemical technologies as they have numerous advantages over classical approaches. While computational support for investigating thermochemical reaction mechanisms is well established, there is still no consistent methodology for modeling electrochemical processes beyond the computational hydrogen electrode. This work addresses this gap through the study of the Shono-type oxidation of N-formylpyrrolidine. Combining density functional theory calculations, the concept of computational Fc⁺/Fc electrode, Marcus–Hush approach, and Butler–Volmer model, the reaction mechanism is elucidated, including the identification of the role and position of proton-coupled electron transfer process. Additionally, simulated cyclic voltammograms are in excellent agreement with experimental studies performed in parallel.