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.
|Commitee:||Dai, Mingji, Thompson, Corey, Wei, Alexander|
|School Location:||United States -- Indiana|
|Source:||DAI-B 80/06(E), Dissertation Abstracts International|
|Subjects:||Chemistry, Inorganic chemistry, Organic chemistry|
|Keywords:||Catalysis, Deoxydehydration, Methodology, Molybdenum, Sulfoxidation|
Copyright in each Dissertation and Thesis is retained by the author. All Rights Reserved
The supplemental file or files you are about to download were provided to ProQuest by the author as part of a
dissertation or thesis. The supplemental files are provided "AS IS" without warranty. ProQuest is not responsible for the
content, format or impact on the supplemental file(s) on our system. in some cases, the file type may be unknown or
may be a .exe file. We recommend caution as you open such files.
Copyright of the original materials contained in the supplemental file is retained by the author and your access to the
supplemental files is subject to the ProQuest Terms and Conditions of use.
Depending on the size of the file(s) you are downloading, the system may take some time to download them. Please be