The development of organic peroxide mediated oxidations

  • Stuart Davidson

Student thesis: Doctoral Thesis

Abstract

This thesis describes the development of two novel metal-free oxidations processes: a method to selective synthesis anti-diols directly from commercially available alkene starting materials and an organocatalytic sulfoxidation procedure using diketones as catalysts.Chapter 1 describes a novel metal-free method for the one-pot anti-dihydroxylation of alkenes to form diols using malonoyl peroxide 13. The reaction conditions were optimised and the scope of the optimal conditions were examined with a variety of stilbene, styrene and indene derivatives to give the corresponding anti-diols in good to excellent yields and selectivities. Following this, a variety of mechanistic investigations were undertaken, revealing key intermediates and allowing the proposal of a mechanism. Scheme 1-1. Optimised conditions of anti-dihydroxylation discussed in Chapter 1. [see thesis for graphic representation]Chapter 2 demonstrates the development of an organocatalytic sulfoxidation using diketone catalysts. Following a significant optimisation process, the scope of sulfoxidation, showing a wide tolerance of functional groups, was explored. Mechanistic investigation was also undertaken, exploring the intermediates isolated from the procedure and an exploration of the reactivity using tool compounds. The stoichiometric process was also investigated to generate kinetics and a postulated transition state. Scheme 1-2. Optimised conditions of organocatalytic sulfoxidation discussed in Chapter 2. [see thesis for graphic representation]Chapter 3 contains the experimental procedures and analytical data generated for all the compounds synthesised within this thesis.
Date of Award1 Apr 2017
LanguageEnglish
Awarding Institution
  • University Of Strathclyde
SponsorsEPSRC (Engineering and Physical Sciences Research Council)
SupervisorNicholas Tomkinson (Supervisor) & John Murphy (Supervisor)

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