This research has been directed at the study of facilitated oxidation of aliphatic sulfides by neighboring group participation. Mesocyclic polythioether and 2-substituted 6-methylthiobicyclo[2.2.1]heptane derivatives have been examined as model compounds for biological redox reactions. The preparations, structural analogues, and oxidation studies of such compounds have been investigated. A new technique has been developed for the preparation of mesocyclic polythioethers. Conformational analysis, both gas phase and solid state, and quantum mechanical analysis of one- and two-electron oxidation of mesocyclic polythioethers have been undertaken. Crystal and molecular structures of some transition metal complexes of 1,4,7-trithiacyclononane, as well as a number of 2-substituted 6-methylthiobicyclo[2.2.1]heptane derivatives have been determined using single crystal X-ray techniques. Stereoselective oxidation of 2-endo-(hydroxymethyl)-6- endo(methylthio)bicyclo[2.2.1]heptane has been achieved leading to both corresponding diastereomeric sulfoxides.
| Identifer | oai:union.ndltd.org:arizona.edu/oai:arizona.openrepository.com:10150/282026 |
| Date | January 1981 |
| Creators | Setzer, William Nathan |
| Contributors | Glass, Richard S. |
| Publisher | The University of Arizona. |
| Source Sets | University of Arizona |
| Language | en_US |
| Detected Language | English |
| Type | text, Dissertation-Reproduction (electronic) |
| Rights | Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. |
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