Synthetic and mechanistic studies of arylsilane oxidation

Thesis

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.

Authors: Rayment, E

• Publication date: 2013
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Keywords: arylsilane; oxidation; phenol
• Subjects: Organic chemistry