A variety of biological and organic reaction mechanisms are studied using
powerful tools from experimental and theoretical chemistry. These tools include the
precise measurement of kinetic isotope effects (KIEs) and the use of theoretical
calculations to predict KIEs as well as determine factors that contribute to reaction
acceleration and selectivity.
Theoretical analysis of the Swain-Schaad relationship involves the prediction of
a large number of isotope effects and establishes the semiclassical boundaries of the
relationship. Studies on the mechanism of oxidosqualene cyclase involve the
determination of a large number of precise KIEs simultaneously. Transition state models
for the Sharpless asymmetric epoxidation have been developed that explain the
versatility, high selectivities, and ligand accelerated catalysis of the reaction. Theoretical
predictions on the proposed enzymatic mechanism of flavin dependent amine oxidation
suggest a hydride transfer mechanism and rules out mechanisms involving covalent
intermediates. Finally, a theoretical analysis of Diels-Alder reactions successfully
describes the unexpected exo selectivity in some of these reactions.
| Identifer | oai:union.ndltd.org:tamu.edu/oai:repository.tamu.edu:1969.1/ETD-TAMU-2446 |
| Date | 15 May 2009 |
| Creators | Hirschi, Jennifer Sue |
| Contributors | Singleton, Daniel A. |
| Source Sets | Texas A and M University |
| Language | en_US |
| Detected Language | English |
| Type | Book, Thesis, Electronic Dissertation, text |
| Format | electronic, application/pdf, born digital |
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