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Utilising Copper for Methodological Advancements in Electro-Organic Synthesis

Seavill, Peter William; (2020) Utilising Copper for Methodological Advancements in Electro-Organic Synthesis. Doctoral thesis (Ph.D), UCL (University College London). Green open access

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Abstract

Electro-Organic Chemistry has great potential to be used extensively in chemical synthesis but remains relatively under-exploited. In an effort to help expand this promising field of research, this PhD project was centred around developing new electrochemical methodology for use in organic reactions, particularly through efficient copper-catalysed processes. Copper(I) acetylides, which are highly useful intermediates found in many organic syntheses, were produced in good to excellent yields and in an energy-efficient manner. This was achieved by using a Cu(0) electrode as the metal source, allowing selective release of Cu(I) ions into solution through an applied oxidative potential. This reaction was expanded upon to incorporate quaternary ammonium salt reduction in an undivided cell to generate a base simultaneously with the Cu(I) ions. Moreover, it proved possible to regenerate the base electrochemically, making the process catalytic in nature. We then incorporated these methods into the pharmaceutically relevant CuAAC reaction, forming C-N bonds. This Cu(0) oxidation was also used to great effect in a catalytic C-C bond-forming reaction, namely Glaser-Hay dimerization, for which an electrochemistry-led mechanistic investigation was carried out to help shed new light on this long-debated reaction, as well as in the Chan-Lam reaction to form C-O bonds. In addition, the development of copper-coated graphite electrodes allowed for control over the amount of copper released in these processes (through the application of Faraday’s laws of electrolysis) and the determination of the oxidation state of the copper released. This system also offered a promising recovery strategy to extract metal ions electrochemically following the completion of reactions, depositing the metal back onto the graphite surface ready to be used again. This has a clear advantage over existing synthetic processes in terms of sustainability and ‘green’ credentials and has great potential utility in environmental chemistry for the minimisation of water pollution.

Type: Thesis (Doctoral)
Qualification: Ph.D
Title: Utilising Copper for Methodological Advancements in Electro-Organic Synthesis
Event: UCL (University College London)
Open access status: An open access version is available from UCL Discovery
Language: English
Additional information: Copyright © The Author 2020. Original content in this thesis is licensed under the terms of the Creative Commons Attribution 4.0 International (CC BY 4.0) Licence (https://creativecommons.org/licenses/by/4.0/). Any third-party copyright material present remains the property of its respective owner(s) and is licensed under its existing terms. Access may initially be restricted at the author’s request.
UCL classification: UCL
UCL > Provost and Vice Provost Offices
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10109676
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