Thesis
The development of metal-free peroxide-mediated chemical reactions
- Creator
- Rights statement
- Awarding institution
- University of Strathclyde
- Date of award
- 2020
- Thesis identifier
- T15927
- Person Identifier (Local)
- 201680854
- Qualification Level
- Qualification Name
- Department, School or Faculty
- Abstract
- This thesis describes the development and optimisation of metal-free alkene difunctionalisation reactions using organic peroxides. An alkene anti-oxyamination procedure has been successfully developed to form protected β-amino alcohols, with an extension of this methodology also giving access to oxazolidinones by an overall alkene syn oxyamination procedure. Additionally, the reactivity of alkenes with a peroxylactone molecule was investigated, with the intention of developing an organocatalytic alkene dihydroxylation procedure. Chapter 1 outlines the previous work conducted within the Tomkinson group concerning alkene functionalisation using organic peroxides. This work includes alkene syn- and antidihydroxylation procedures using a malonoyl peroxide, intramolecular alkene functionalisation to access nitrogen and oxygen containing heterocycles and an organocatalytic sulfoxidation procedure. Chapter 2 describes the discovery and development of a novel alkene anti-oxyamination reaction using a malonoyl peroxide. Following discovery and an optimisation of a suitable nitrogen nucleophile, the scope of the reaction was investigated, showing excellent yield and diastereoselectivity. Oxyaminated products were successfully deprotected, providing handles for further functionalisation. Finally, the methodology was further developed to access oxazolidinone molecules by a formal alkene syn-oxyamination procedure. Chapter 3 describes the novel reactivity of a peroxylactone molecule with alkenes. The primary reaction was found to be an epoxidation, with the resulting epoxide reacting further to give numerous additional products. A mechanistic investigation was conducted to explain the formation of each reaction product observed. Based upon this knowledge attempts were made to control the reaction towards a selective dihydroxylation procedure, with an optimisation of conditions and substrate engineering. Chapter 4 contains the experimental procedures and characterisation for the relevant compounds found within this thesis.
- Advisor / supervisor
- Tomkinson, Nick.
- Resource Type
- Note
- This thesis was previously held under moratorium from 3rd August 2021 to 3rd October 2022.
- DOI
- Embargo Note
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