Thesis
Exploring radical-mediated processes for the development of novel methodologies and technologies
- Creator
- Rights statement
- Awarding institution
- University of Strathclyde
- Date of award
- 2023
- Thesis identifier
- T17439
- Person Identifier (Local)
- 201979053
- Qualification Level
- Qualification Name
- Department, School or Faculty
- Abstract
- Chapter 1: A previously reported C–H amination by Leonori et al. described the transformation occurring in presence and the absence of light, however the ‘dark’ reaction was not exploited in the report. Running control reactions which were exposed to air revealed the conversion of the reaction could be improved. The reaction was shown to run in the absence of Ru(bpy)3Cl2 as an additive, however consistently higher yields were achieved when it was present in the reaction mixture. The first examples of non-photochemical radical-mediated intramolecular C–H amination are demonstrated, affording 1-methyl-1,2,3,4-tetrahydroquinoline derivatives. [See thesis text for illustrative Figure 1]. Aspects of the reaction mechanism have been explored computationally and experimentally, which have led to the proposal of the formation of dicationic intermediates which fragments to a nitrogen-centred radical which can react with (hetero)arenes. [See thesis text for illustrative Figure 2]. Chapter 2: The combination of Et3SiH and KOtBu (also known as the Grubbs-Stoltz reagent) gives rise to a number of reactive intermediates which can participate in both polar and radicalmediated pathways: single electron transfer, hydride transfer and hydrogen-atom transfer. Following on from the discovery of an intermolecular alkylation of diarylmethanes in ether solvents (THF or 1,4-dioxane), a novel deoxygenative intramolecular alkylation was developed. Synthesis of a number of hydroxypropyl derivatives led to the corresponding cyclopropane products. Some substrates gave rise to over-reduced products, for which plausible mechanisms to their formation are suggested. [See thesis text for illustrative Figure 3]. Chapter 3: The development of a novel photochemical flow reactor with Taylor-Couette flow was pursued as part of an ongoing collaboration with Autichem Ltd. As the reactor is a prototype, it was fully characterised with Villermaux-Dushman mixing studies and residence time distribution measurements. The DART reactor was further characterised by the evaluation of benzylic bromination examples, to generate intermediates that are of pharmaceutical relevance in the synthesis of APIs and in one example, >300 g of material was processed. [See thesis text for illustrative Figure 4].
- Advisor / supervisor
- Murphy, John A.
- Fenner, Sabine
- Resource Type
- Note
- Previously held under moratorium in Chemistry department (GSK) from 4th July 2023 until 15th August 2025. The confidentiality statement on each page of this thesis DOES NOT apply
- DOI
- Funder
- Embargo Note
关系
项目
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File | 2025-08-15 | 限制运用 |