Date of Award:

5-2013

Document Type:

Dissertation

Degree Name:

Doctor of Philosophy (PhD)

Department:

Chemistry and Biochemistry

Committee Chair(s)

Lisa M. Berreau

Committee

Lisa M. Berreau

Committee

Alvan C. Hengge

Committee

John L. Hubbard

Committee

Paul R. Grossl

Committee

Bradley S. Davidson

Abstract

The work presented in this dissertation has focused on the activation and cleavage of chemical bonds between two carbon atoms. The selective oxidative activation of carbon-carbon bonds is important due to potential applications in the utilization of biomass for fuel production, applications in wastewater treatment and bioremediation, and in developing new reactions for organic synthesis of fine chemicals including pharmaceuticals. Ideally these reactions would be carried out with high atom economy at low temperatures and pressures, and using earth-abundant elements as reagents and catalysts. With these points in mind, nature provides an ideal model framework, carrying out its chemistry at ambient temperature and pressure. Enzymes that cleave C-C bonds by a dioxygenolytic pathway have been our focus as they utilize dioxygen as a terminal oxidant and also do not require any coreductants, maximizing atom economy.

Our strategy has been to use small molecular models to study complex biological systems or, conversely, to take inspiration from highly active biological systems to design new ways to activate small molecules. We have focused on exploring the reaction pathways of several dioxygenase enzymes that cleave aliphatic C-C bonds, with the goal of understanding fundamental factors involved in the activation and direction of cleavage of these bonds. These efforts have led to several important advances in understanding of the cleavage of C-C bonds. Additionally, the work presented here has thus far led to five peer-reviewed publications and five presentations at scientific conferences across the country.

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