Dialling-In New Reactivity into the Shono-type Anodic Oxidation Reaction

This Personal Account describes the author's groups' research in the field of electrosynthetic anodic oxidation, beginning with initial trial and error attempts with the Shono oxidation. Early setbacks with complex rotameric amide mixtures, provided the ideal environment for the discovery of the Oxa-Shono reaction-O-sp(2)-C-sp(3) bond cleavage of esters-providing two useful products in one-step: aldehyde selective oxidation level products and a mild de-esterification method to afford carboxylic acids in the process. The development of the Oxa-Shono reaction provided the impetus for the discovery of other electrically propelled-N-sp(2)-C-sp(2) and N-sp(2)-C-sp(3)-bond breaking reactions in bioactive amide and sulfonamide systems. Understanding the voltammetric behaviour of the molecule under study, switching between controlled current- or controlled potential- electrolysis, and restricting electron flow (the reagent), affords exquisite control over the reaction outcomes in batch and flow. Importantly, this bio-inspired advance in electrosynthetic dealkylation chemistry mimics the metabolic outcomes observed in nature.

Automated summary

This study describes the author's research on electrosynthetic anodic oxidation, focusing on the discovery of the Oxa-Shono reaction and its applications in selective oxidation and de-esterification processes. This bio-inspired advance in dealkylation chemistry provides exquisite control over reaction outcomes and mimics metabolic processes observed in nature.