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Peroxides as Sources of Electrophilic Oxygen: Their Reactivity and Synthesis
Peroxides can be used as a source of electrophilic oxygen per the 1925 discovery by Gilman and Adams that Grignard reagents could be reacted with various peroxides to form carbon-oxygen bonds. This report further explores the electrophilicity of peroxides by studying their reactions with various nucleophiles. In this dissertation one will find multiple synthetic approaches to peroxides including the historically straightforward but also the synthesis of two new classes of materials: trifluoromethyl peresters and trifluoromethyl persulfonates. Also found here is a discussion of the reactivity of such materials. Specifically, the intramolecular reaction of peroxides to form strained bicyclic ethers will be featured heavily both as an advance in methodology development but also with the goal of applying said methodology to the synthesis of the thromboxane A2, a member of the eicosanoid family. Intermolecular reactions have also been explored here in two major ways: first the discovery of alkoxide assistance in intermolecular couplings of stabilized anions and simple peroxides as well as the discovery of a trifluoromethoxy transfer reagent. Further, an overview of perester chemistry and the exploration of ionone derivatives for ubiquitinase inhibition is featured here.
Locklear, Moriah, "Peroxides as Sources of Electrophilic Oxygen: Their Reactivity and Synthesis" (2020). ETD collection for University of Nebraska - Lincoln. AAI27956022.