The experimental and theoretical determination of combinatorial kinetic isotope effects for mechanistic analysis
dc.contributor.advisor | Singleton, Daniel A. | |
dc.creator | Christian, Chad F. | |
dc.date.accessioned | 2010-01-15T00:00:19Z | |
dc.date.accessioned | 2010-01-16T01:32:39Z | |
dc.date.available | 2010-01-15T00:00:19Z | |
dc.date.available | 2010-01-16T01:32:39Z | |
dc.date.created | 2007-05 | |
dc.date.issued | 2009-05-15 | |
dc.identifier.uri | https://hdl.handle.net/1969.1/ETD-TAMU-1253 | |
dc.description.abstract | Unfortunately, chemists can never experimentally unravel a full reaction pathway. Even our ability to define key aspects of mechanisms, such as short-lived intermediates and the even more ephemeral transition states, is quite limited, requiring subtle experiments and subtle interpretations. Arguably the most important knowledge to be gained about the mechanism of a reaction is the structure and geometry of the transition state at the rate-limiting step, as this is where a reaction’s rate and selectivity are generally decided. The Singleton group has developed a methodology for predicting the combinatorial kinetic isotope effects (KIEs) at every atomic position, typically carbon or hydrogen, at natural abundance. A combination of experimental isotope effects and density functional theory (DFT) calculations has greatly aided our ability to predict and understand a reaction’s pathway and transition state geometries. Precise application of this method has allowed for the mechanistic investigation of a myriad of bioorganic, organic, and organometallic reactions. The technique has been applied in the analysis of the catalytic borylation of arenes via C-H bond activation, dynamic effects in the enyne allene cyclization, palladium catalyzed allylic alkylation, the nature of proton transfer in orotate decarboxylase, and the epoxidation of enones with t-butyl hydroperoxide. | en |
dc.format.medium | electronic | en |
dc.format.mimetype | application/pdf | |
dc.language.iso | en_US | |
dc.subject | Isotope Effects | en |
dc.subject | Mechanisms | en |
dc.title | The experimental and theoretical determination of combinatorial kinetic isotope effects for mechanistic analysis | en |
dc.type | Book | en |
dc.type | Thesis | en |
thesis.degree.department | Chemistry | en |
thesis.degree.discipline | Chemistry | en |
thesis.degree.grantor | Texas A&M University | en |
thesis.degree.name | Doctor of Philosophy | en |
thesis.degree.level | Doctoral | en |
dc.contributor.committeeMember | Bergbreiter, David E. | |
dc.contributor.committeeMember | LiWang, Andy | |
dc.contributor.committeeMember | Raushel, Frank M. | |
dc.type.genre | Electronic Dissertation | en |
dc.type.material | text | en |
dc.format.digitalOrigin | born digital | en |
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