Use this URL to cite or link to this record in EThOS: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.692846
Title: Synthetic and mechanistic studies of arylsilane oxidation
Author: Rayment, Elizabeth
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2013
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Abstract:
In this thesis, we study arylsilane oxidation from both a synthetic and a mechanistic perspective. Building upon previous work within our group, we demonstrate in an early chapter that arylhydrosilanes are surprisingly reactive to oxidation. This disproves the previous assumptions of the Tamao oxidation and provides new insights into the mechanism of the reaction. Furthermore, we find that the best substrates for oxidation are arylmethoxysilanes, and we describe rapid and efficient syntheses for these compounds. A further chapter addresses applications of arylsilane oxidation to natural product synthesis, protecting group chemistry and cycloadditions. By collecting concentration profiles of the oxidation of various arylsilanes, we reveal a rapid equilibration between arylmethoxysilanes and arylsilanols. By comparison, phenol formation (especially from silanol) is often slow. The rate of oxidation turns out to be highly sensitive to both the concentration of the oxidising agent and the substituents of the aromatic ring. In the final chapter we discuss in detail the consequences of these observations for the mechanism of arylsilane oxidation.
Supervisor: Anderson, Edward Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.692846  DOI: Not available
Keywords: Organic chemistry ; arylsilane ; oxidation ; phenol
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