Date

2015

Document Type

Dissertation

Degree

Doctor of Philosophy

Department

Chemistry

First Adviser

Flowers, Robert A.

Other advisers/committee members

Vicic, David; Pires, Marcos; Kuchka, Michael

Abstract

Catalytic oxidations that proceed through single-electron transfers are emerging as important approaches towards the formation of C-C and C-F bonds in molecules of pharmaceutical and biological importance. A great deal of recent effort has focused on metal-catalyzed oxidations, in particular silver catalysis combined with the use of a terminal oxidant. In addition, the use of readily available starting materials employed in these reactions can provide a wide range of structures important for screening in medicinal chemistry and for the construction of building blocks important in materials chemistry. The motivation for this research lies in the fundamental understanding of electron transfer in metal-mediated organic reactions. A greater understanding of the mechanistic pathways in these reactions can allow for the optimization of existing methods, as well as opening up the possibility for the development of new synthetic reactions.The research presented in this dissertation encompasses the mechanistic studies of several silver-catalyzed reactions of synthetic importance that are thought to go through single electron oxidation. This work has led to a greater understanding of (a) carbon-carbon bond formation between arylboronic acids and heteroarenes mediated by persulfate, (b) the coupling of arylboronic acids to quinones, (c) alkyl fluorinations that proceed through decarboxylation in aqueous media, and (d) the development and mechanistic study of a decarboxylative fluorination in organic media through the use of a sterically-hindered ligand. Investigations of these reactions have revealed considerable amounts of unexpected mechanistic complexity. The mechanistic studies and method development of these reactions has led to the development of more efficient catalytic single-electron oxidation reactions, and has the potential to influence new areas of synthetic and organometallic chemistry.

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