Dialling‐In New Reactivity into the Shono‐Type Anodic Oxidation Reaction

Abstract

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‐Osp2‐Csp3 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‐Nsp2‐Csp2 and Nsp2‐Csp3‐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.

Computational Predictive and Electrochemical Detection of Metabolites (CP-EDM) of Piperine

“…Having established that piperine is both electrochemically active and has multiple oxidation events, we then employed our established protocols for Shono-type [31][32][33][34][35] and Oxa-Shono-type oxidations. [36] Piperine was reacted under electrochemical conditions and the series of products resulting were analysed by LC-MS (Scheme 1 and Figure 2).…”

A General Method to Access Underexplored Ylideneamino Sulfates as Interrupted Beckmann-Type Rearrangement Intermediates

“…The Beckmann rearrangement has been modified and updated using catalysts [7,8], acidic ionic liquids [9][10][11], radicals [12], photochemistry [13], reagent improvements [14,15], and recently, an example of an interrupted Beckmann rearrangement [16]. In turn, the amides generated are important substrates for electrosynthesis applications [17][18][19][20].…”

Electrochemical Synthesis of Added Valuable Purine Alkaloid Metabolites from Caffeine Feedstock Employing a Structure Electro-Activity Relationship (SeAR) Approach

“…[9][10] The use of electrochemistry to generate information on drug metabolites is a rapidly developing method of importance for establishing environmental fate. [11][12][13][14][15][16][17][18][19][20] In this study, we considered whether the application of electrochemistry [21][22][23][24][25][26] would achieve the single step synthesis of authentic caffeine metabolites and a predictive structure electroactivity relationship (SeAR) model for metabolism.…”