Date of Award
Doctor of Philosophy (PhD)
Committee Member 1
Committee Member 2
Molybdenum-centered enzymes occur naturally throughout a variety of organisms. These enzymes have shown interesting reactivities, including oxygen atom transfer reactions. As such, there has been a great deal of interest in creating synthetic analogs of these complexes to further probe the reactive properties of molybdenum catalysts. This work focuses on designing and synthesizing molybdenum complexes for oxygen atom transfer reactions. The first chapter will discuss the design, synthesis, and characterization of three molybdenum dioxo complexes used in sulfoxidation reactions. It will also discuss the development of this reaction methodology, as well as cover substrate scope and application to total synthesis and industry. The second chapter still focuses on these three catalysts, but now examines the kinetic and mechanistic probing of the sulfoxidation reactions. Chapter four discusses a different molybdenum dioxo complex that was discovered to be effective in deoxydehydration reactions. The methodology development is discussed with a focus on substrate tolerance of the catalyst. This section attempts to probe the mechanism of the reaction to propose a reasonable catalytic cycle. The final chapter shifts from organometallic synthesis to organic synthesis. In this section, the development of a novel methodology for the synthesis of 8-membered cyclic ethers, called oxocines, is discussed. This is of interest for two reasons. First, these medium-sized rings are generally synthetically difficult to access. Second, these particular scaffolds are observed in a variety of natural products that have shown biological activity
Cantwell, Kelsey, "Design and Synthesis of Molybdenum-Dioxo Complexes and the Development of Novel Methodologies" (2017). Open Access Dissertations. 1529.