Studies directed towards the synthesis of irroratin A and studies directed towards the synthesis of rocaglamide and silvestrol
| dc.contributor.advisor | Magnus, Philip D. | en |
| dc.creator | Rainey, Trevor James | en |
| dc.date.accessioned | 2008-08-28T23:09:20Z | en |
| dc.date.available | 2008-08-28T23:09:20Z | en |
| dc.date.issued | 2006 | en |
| dc.description | text | en |
| dc.description.abstract | Studies directed towards the total synthesis of the cytotoxic ent-kaurane diterpene irroratin A were carried out. In a model system it was found that Pummerer cyclization gave a bicyclo[2.2.2]octane whereas activation as an allylsilane gave the desired [3.2.1]- bicycle. In a more functionalized system, the use of a rhodium-catalyzed C-H insertion reaction allowed for ready access to the bicyclo[3.2.1]octan-6-one core structure. Attempts to construct the remainder of irroratin A utilizing this core structure were ultimately unsuccessful. The use of a Nazarov reaction for the diastereoselective synthesis of silvestrol and rocaglamide was also studied. A model compound lacking the 6,8-oxygenation present in the natural products was synthesized and subjected to a variety of Lewis and Brønsted acids; in all cases no Nazarov cyclization was observed, but rather (typically) retro Friedel-Crafts acylation. In an attempt to bias the reaction towards the desired pathway more activated substrates were made; however, cyclization was again unsuccessful. | |
| dc.description.department | Chemistry and Biochemistry | en |
| dc.description.department | Chemistry | en |
| dc.format.medium | electronic | en |
| dc.identifier | b65489639 | en |
| dc.identifier.oclc | 156943742 | en |
| dc.identifier.uri | http://hdl.handle.net/2152/2797 | en |
| dc.language.iso | eng | en |
| dc.rights | Copyright is held by the author. Presentation of this material on the Libraries' web site by University Libraries, The University of Texas at Austin was made possible under a limited license grant from the author who has retained all copyrights in the works. | en |
| dc.subject.lcsh | Irroratin A--Synthesis | en |
| dc.subject.lcsh | Rocaglamide--Synthesis | en |
| dc.subject.lcsh | Silvestrol--Synthesis | en |
| dc.title | Studies directed towards the synthesis of irroratin A and studies directed towards the synthesis of rocaglamide and silvestrol | en |
| dc.type.genre | Thesis | en |