Date of Award

2015

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Matthias Brewer

Abstract

The fragmentation of γ-silyloxy-β-hydroxy-α-diazoesters to provide tethered aldehyde ynoates was discovered and developed in Prof. Brewer's laboratory. This reaction is a Lewis acid mediated heterolytic cleavage of the Cβ-γ bond of a γ-silyloxy-β-hydroxy-α-diazocarbonyl functional group array contained in a ring compound.

This dissertation describes a further study of this ring fragmentation reaction and application of this fragmentation to the preparation of synthetically useful organic molecules. The purpose of this dissertation work was three fold. The first objective was to extend this ring fragmentation reaction to the synthesis of tethered aldehyde ynones by fragmenting various γ-silyloxy-β-hydroxy-α-diazo ketone compounds. The second objective was to develop a new way to make medium size rings by fragmenting fused bicyclic γ-silyloxy-β-hydroxy-α-diazo ketones. The final goal was to use this reaction to make medium size ynolides by fragmentation of fused bicyclic γ-silyloxy-β-hydroxy-α-diazo esters to provide core structures for medium-size lactones which are synthetically challenging to make using other available methods.

Language

en

Number of Pages

375 p.

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