Synthetic organic electrochemistry to develop new transformations involving radical intermediates

Harnedy, James 2023. Synthetic organic electrochemistry to develop new transformations involving radical intermediates. PhD Thesis, Cardiff University. Item availability restricted.

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Abstract

This thesis describes efforts to develop novel synthetic transformations enabled by electrochemistry. Chapter one of this thesis aims to introduce some fundamentals of synthetic electrochemistry and exhibit its’ application to synthesis. Chapter two of this thesis covers efforts to explore electrochemical alkene functionalisation, more specifically the Z-selective functionalisation of acrylamides, and aims to demonstrate why the developed electrochemical transformation is useful in synthesis. To this end, the transformation was demonstrated on a range of substrates, orthogonal derivatisations of the product were carried out and the reaction was scaled up using an electrochemical flow reactor. Chapter three of this thesis builds upon a core research interest of the Morrill group, namely the generation and utilisation of O-centred radicals. The key investigation described in this work was the electrochemical generation of alkoxy radicals to access 1,5-hydrogen atom transfer reactivity, an underexplored area. A model system based on a 1,5-HAT and functional group migration cascade was targeted and systematic investigations resulted in moderate success. Finally, chapter four of this thesis describes a novel approach for the deconstructive functionalisation of cycloalkanols. In this study, the mesolytic cleavage of electrochemically generated aryl radical cations is used to ring opening cyclic alcohols and allow for distal functionalisation with nucleophiles. The scope of this transformation was explored through systematic substrate variation and the use of a variety of O and N-centred nucleophiles. Comprehensive mechanistic studies have been carried out, using synthetic and computational approaches, and the reaction was scaled up using electrochemical flow.

Item Type:	Thesis (PhD)
Date Type:	Completion
Status:	Unpublished
Schools:	Chemistry
Date of First Compliant Deposit:	22 January 2024
Last Modified:	22 Jan 2025 02:30
URI:	https://orca.cardiff.ac.uk/id/eprint/165705

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