The development of a metal-free catalytic method for the selective hydroxylation of aliphatic C-H bonds
Abstract/Contents
- Abstract
- The diversity and structural intricacies of molecules needed for pharmaceutical, biological, and materials applications have challenged chemists to develop transformative chemical processes that greatly facilitate small molecule synthesis. C-H Bond functionalization represents one such class of reaction types, and is a general problem for reaction discovery that has witnessed an explosion of interest within the past 10 years. Inspired largely by Nature's ability to conduct site- and stereoselective C-H bond oxidation reactions, we have been driven to design small molecule catalysts that can emulate such processes. Our focus has taken aim at the problem of C-H bond hydroxylation, efforts that have yielded a novel, non-metal-based catalytic system for the selective oxidation of tertiary C-H bonds. These findings contrast the large body of literature detailing C-H hydroxylation reactions through transition-metal mediated catalysis. 1,2,3-Benzoxathiazine-2,2-dioxide-based heterocycles have been shown to function as catalysts for C-H hydroxylation with hydrogenperoxide operating as the terminal oxidant. The evolution of this catalytic process, which capitalizes on the unique reactivity of an oxaziridine intermediate, was made possible using density functional theory to help guide reagent design. In addition, kinetic analysis of the stoichiometric oxygen-atom transfer reaction has provided insight into the principal features that influence oxaziridine reactivity. This information coupled with the discovery that reactions could be conducted under aqueous reaction conditions with hydrogenperoxide has resulted in a markedly improved process for tertiary C-H hydroxylation. The reaction occurs stereospecifically and with predictable chemoselectivity in substrates possessing more than one tertiary C-H center. The enhanced performance of this catalytic process has been ascribed to the hydrophobic aggregation of the benzoxathiazinane catalyst and hydrocarbon substrate, which serves to accelerate the kinetically slow hydroxylation event.
Description
| Type of resource | text |
|---|---|
| Form | electronic; electronic resource; remote |
| Extent | 1 online resource. |
| Publication date | 2010 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Associated with | Litvinas, Nichole Danielle |
|---|---|
| Associated with | Stanford University, Department of Chemistry |
| Primary advisor | Du Bois, Justin |
| Advisor | Waymouth, Robert M |
| Advisor | Wender, Paul A |
| Thesis advisor | Waymouth, Robert M |
| Thesis advisor | Wender, Paul A |
Subjects
| Genre | Theses |
|---|
Bibliographic information
| Statement of responsibility | Nichole Danielle Litvinas. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Thesis (Ph.D.)--Stanford University, 2010. |
| Location | electronic resource |
Access conditions
- Copyright
- © 2010 by Nichole Danielle Litvinas
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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