Dialling-in new reactivity into the Shono-type anodic oxidation reaction

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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.
Original languageEnglish
Pages (from-to)2120-2129
JournalThe Chemical Record
Volume21
Issue number9
Early online date4 Nov 2020
DOIs
Publication statusPublished - Sep 2021

Bibliographical note

None of this would have been possible without a diverse team of talented co-workers, critical funding, and chance meetings to which I am grateful to all. This includes; Paulino Alfonso Suárez, Mohammed Ali Abdullahi, Mateus dos Reis Barone, Mandeep K. Bal, Shilpa Pradeep, Daniel Miles-Barrett, Rebecca Hawkins, Muhammad (Habib) Rahman, Annica Wetzel and Hikari Fuchigami. I thank the following funders: Royal Society, London (UK) for the award of a starter research grant (RG150135), the Erasmus+ staff mobility scheme for funding a productive exchange with Prof. Wes R. Browne (University of Groningen, NL), the Erasmus+ and British Council student scheme for making possible the visits of many talented researchers to my laboratory (Paulino Alfonso-Suarez, Mohammed Ali Abdullahi), and UNESP, Sao Paulo (Mateus dos Reis Barone). I am indebted to the RKE Research Accelerator Grant, Dalton Research Institute, and EMRC research grant for supporting my first post-graduate student (Mandeep K. Bal). I would also like to thank Manchester Metropolitan University (UK) for the initial start-up support given to my group, and The University of Birmingham (UK) for equipment funds that grew the project, Cambridge Reactor Design (Dr Bahir Hajj, Cambridge, UK) for supporting our investigations of electrosynthesis in-flow with the Ammonite8 reactor. Finally, to all of those who shared their knowledge, challenged our understanding or gave advice at key junctures in the progress of this work: Prof. Craig Banks (MMU, UK), Prof. Wesley Browne (University of Groningen, The Netherlands), Prof. Richard Brown (University of Southampton, UK), Prof. David Proctor (University of Manchester, UK), Dr James Donald (University of York, UK), Dr Simon Lewis (University of Bath, UK) and Dr Anthony Green (University of Manchester, UK).

Keywords

  • Anodic oxidation
  • bond cleavage
  • dealkylation
  • electrosynthesis
  • Shono
  • Materials Chemistry
  • General Chemistry
  • General Chemical Engineering
  • Biochemistry

ASJC Scopus subject areas

  • Materials Chemistry
  • Chemical Engineering(all)
  • Chemistry(all)
  • Biochemistry

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