New processes that leads to formation of new carbon-carbon bond (the Michael reaction, the Mannich reaction and alkylation reaction) or carbon-heteroatom bond (á-halogenation, á-hydroxylation and á-amination) on bridged bicyclic ketones such as tropinone and TBON were investigated, utilizing LDA in the deprotonation step. All reactions, in which new carbon-heteroatom bond is formed, were not successful either due to low selectivity and/or yields. In case of new carbon-carbon bond forming processes, careful choice of electrophile (electrophile having the ester group in á-position to leaving group), allows for alkylation of tropinone with moderate yield and good selectivity.
Application of new conditions to the aldol reaction of TBON and tropinone (e.g. MgI2 catalyzed aldol reaction), gave new aldol products that were not detected from the lithium enolate chemistry of these ketones. Modification of reaction conditions in case of MgI2 catalyzed aldol reaction provides, in a one pot process, bis-aldol product from TBON in good yield and high selectivity, as a single diastereoisomer.
Finally, TBON is used as a suitable scaffold for the synthesis of thiacocaine. The first known synthesis of racemic thiacocaine is presented, via deprotonation of TBON with LDA, as a key step.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:SSU.etd-11152008-155706 |
| Date | 19 November 2008 |
| Creators | Sikorska, Laura |
| Contributors | BALSEVICH, JOHN, MICHEL, GRAVEL, LEE, WILSON, MAREK, MAJEWSKI |
| Publisher | University of Saskatchewan |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | http://library.usask.ca/theses/available/etd-11152008-155706/ |
| 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 Saskatchewan 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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