Thesis

Metal-free oxidation of unactivated sp3 C–H bonds.

Creator
Rights statement
Awarding institution
  • University of Strathclyde
Date of award
  • 2021
Thesis identifier
  • T16135
Person Identifier (Local)
  • 201688984
Qualification Level
Qualification Name
Department, School or Faculty
Abstract
  • This report describes work carried out on the oxidation of unactivated sp3 C–H bonds. The methodology developed is easy to execute, requiresthe commonly available oxidant mCPBA, and can be performed without specialised equipment or techniques. CHAPTER ONE consists of the analysis of the challenges associated with unactivated sp3 C–H bond oxidation is provided. An overview of currently available methods for unactivated sp3 C–H bonds oxidation. The methodologies reviewed include: heterogeneous metal catalysis, homogeneous metal catalysis, functional group directed C–H functionalisation, indirect activation by metal complexes, enzymatic oxidation, biomimetic catalysis, and metal-free oxidants. CHAPTER TWO describes the theoretical basis of the project, a recap of the results of a mechanistic investigation from research carried out previously within the group and, an analysis of potential directions of contribution to existing research. CHAPTER THREE describes the development of a novel ketene-based approach for unactivated sp3 C–H bond oxidation. Identification of conditions for reagentless in situ ketene formation as well as isolation of an alternative ketene structure is described. Experiments of the enolisation of organic peracids revealed no evidence for the occurrence of the event and an enolisable carbon was found to be unnecessary for the transformation. CHAPTER FOUR describes an investigation of novel conditions for conducting peracid-induced oxidation of unactivated sp3 C–H bonds. Extensive reaction condition optimisation was conducted to achieve high yield and selectivity using the commercially available oxidant mCPBA. Kinetic investigation into an observed solvent effect in conjunction with DOSY experiments allowed the establishment of the step in the oxidation sequence which was affected by the solvent. CHAPTER FIVE describes the development of a computational model to support the project. This model provided a rationale for the observed experimental outcomes. Close replication of substituent effects of the peracid structure and the environment of the C–H bond undergoing oxidation, allowed us to obtain predictive capacity. An explicit solvation model closely replicated the kinetic results obtained in Chapter Four. CHAPTER SIX contains a summary of the conducted research. CHAPTER SEVEN contains a proposal for future research. CHAPTER EIGHT details the experimental procedures, computational geometries as well as X-ray crystallography data. CHAPTER NINE contains the bibliography.
Advisor / supervisor
  • Tomkinson, Nicholas C. O.
Resource Type
Note
  • This thesis was previously held under moratorium from 17th January 2022 until 17th January 2024.
DOI
Embargo Note
  • ACCESS TO THE DIGITAL COPY OF THIS THESIS IS RESTRICTED TO STRATHCLYDE USERS ONLY UNTIL 17TH JANUARY 2027.

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