Electrochemical deconstructive functionalisation of arylalcohols via fragmentation of anodically generated aromatic radical cations-a synthetic and mechanistic investigation

Maashi, Hussain 2025. Electrochemical deconstructive functionalisation of arylalcohols via fragmentation of anodically generated aromatic radical cations-a synthetic and mechanistic investigation. PhD Thesis, Cardiff University. Item availability restricted.

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Abstract

This thesis describes synthetic and mechanistic investigations into the development of new electrochemical deconstructive functionalisation methodologies applicable to organic synthesis. The first chapter of this thesis introduces the fundamentals of synthetic electrochemistry, highlights the basic requirements and demonstrates its application to organic synthesis. The second chapter demonstrates the discovery and development of a novel approach for the deconstructive functionalisation of cycloalkanols via the mesolytic cleavage of anodically generated aromatic radical cations. In this study, alcohols, N-heterocycles, and fluoride are employed as nucleophiles. The approach has been demonstrated across a broad range of cycloalkanol substrates to access useful remotely functionalised ketone products. The third chapter this thesis demonstrates mechanistic investigation of the synthetic approach described in the second chapter. Synthetic, electroanalytical, and computational studies were conducted to understand the reaction mechanism and structural requirements for fragmentation. It was found that arylalcohols undergo anodic oxidation, generating aromatic radical cations that fragment into oxocarbenium ions and radical intermediates. The transformation is promoted by structural features that stabilise these intermediates. This understanding is expected to facilitate the development of alternative electrosynthetic transformations utilising this mode of substrate activation. The fourth chapter of this thesis demonstrates an alternative electrosynthetic transformation utilising the synthetic approach developed and investigated in the previous chapters. The approach is used for the synthesis of C(sp3 )-rich heterocycles via the mesolytic cleavage of anodically generated aromatic radical cations and the trapping of formed carbocation intermediates with internal nucleophiles. The method has been demonstrated across various arylalcohol substrates to access a diverse range of heterocycles including tetrahydrofuran, tetrahydropyran, and pyrrolidine scaffolds. The electrochemical method was demonstrated on a 5 mmol scale via single pass continuous flow, which utilised lower supporting electrolyte concentration and exhibited increased productivity in relation to the batch process.

Item Type:	Thesis (PhD)
Status:	Unpublished
Schools:	Schools > Chemistry
Date of First Compliant Deposit:	25 July 2025
Last Modified:	25 Jul 2025 15:52
URI:	https://orca.cardiff.ac.uk/id/eprint/180041

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