[4+1] cyclopentene annulation in the total synthesis of pentalenene type sesquiterpenes
| dc.contributor.author | Natchus, Michael George | en |
| dc.contributor.department | Chemistry | en |
| dc.date.accessioned | 2014-08-13T14:40:17Z | en |
| dc.date.available | 2014-08-13T14:40:17Z | en |
| dc.date.issued | 1987 | en |
| dc.description.abstract | The generality of the [4+1] cyclopentene annulation was demonstrated by the total synthesis of (±)-pentalenene and its C-9 epimer which were prepared in a stereocontrolled manner in analogy with the synthesis of (±)-isocomene, (±)-hirsutene and (±)-pentalenic acid. The key features of this synthesis involved preparation of acid 161, its conversion to diazoketone 148, intramolecular cyclopropanation of this substance to vinylcyclopropane 163 and the vinylcyclopropane-cyclo pentene rearrangement of several derivatives of 195 to triquinanes 147, 146, 197, and 204. A detailed study of temperature, conformation, and electronic effects on the diradical scission of vinylcyclopropanes of type 195 was carried out under pyrolytic conditions. Conclusive results regarding conformational stability at C-9 were also attained and exploited in the context of stereocontrol at this center. As a result of this synthesis, several new methods of functional transformations emerged, such as the selective reduction of conjugated esters and a new method of preparation of enolethers from carboxylic acids. | en |
| dc.description.admin | incomplete_metadata | en |
| dc.description.degree | Master of Science | en |
| dc.format.extent | v, 164 leaves | en |
| dc.format.mimetype | application/pdf | en |
| dc.identifier.uri | http://hdl.handle.net/10919/50070 | en |
| dc.publisher | Virginia Polytechnic Institute and State University | en |
| dc.relation.isformatof | OCLC# 17604852 | en |
| dc.rights | In Copyright | en |
| dc.rights.uri | http://rightsstatements.org/vocab/InC/1.0/ | en |
| dc.subject.lcc | LD5655.V855 1987.N372 | en |
| dc.subject.lcsh | Organic compounds -- Synthesis | en |
| dc.title | [4+1] cyclopentene annulation in the total synthesis of pentalenene type sesquiterpenes | en |
| dc.type | Thesis | en |
| dc.type.dcmitype | Text | en |
| thesis.degree.discipline | Chemistry | en |
| thesis.degree.grantor | Virginia Polytechnic Institute and State University | en |
| thesis.degree.level | masters | en |
| thesis.degree.name | Master of Science | en |
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