Ketenes are molecules containing a carbonyl group connected to an alkylidene group by way of a double bond (a pi-bond). The electrophilic nature of ketenes at their center, sp-hybridized carbon atom is the origin of many of the chemical transformations availible to these molecules. Previously in the Nelson laboratory, ketenes had been successfully employed in the acyl halide-aldehyde cyclocondensation (AAC) reaction. Both Lewis acid- and Lewis base-catalyzed AAC processes provide access to optically active 3,4-disubstituted-syn-2-oxetanones. The work described herein employs ketene in the Lewis base-catalyzed AAC reaction in an attempt to improve and expand the general utility of this reaction technology. This improved AAC methodology was then applied in the total synthesis of the natural product motuporin. Ketene was subsequently employed in the development of a novel ketene-Claisen rearrangement.
| Identifer | oai:union.ndltd.org:PITT/oai:PITTETD:etd-12012005-162855 |
| Date | 20 March 2006 |
| Creators | Raelin, Jeremy M |
| Contributors | Dr. Scott G. Nelson, Dr. Peter Wipf, Dr. Craig S. Wilcox |
| Publisher | University of Pittsburgh |
| Source Sets | University of Pittsburgh |
| Language | English |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | http://etd.library.pitt.edu/ETD/available/etd-12012005-162855/ |
| Rights | unrestricted, I hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to University of Pittsburgh or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report. |
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