Stereoselective syntheses of functionalized tetrahydrofurans via intramolecular oxymetallations of allenes and syntheses of methyl nonactate homologues
| dc.creator | Park, Gyoosoon | |
| dc.date.accessioned | 2016-11-14T23:09:46Z | |
| dc.date.available | 2011-02-18T23:55:21Z | |
| dc.date.available | 2016-11-14T23:09:46Z | |
| dc.date.issued | 1988-12 | |
| dc.degree.department | Chemistry | en_US |
| dc.description.abstract | My research objective was to investigate two-step intramolecular nucleometallationcoupling reactions of allenes to form polyfiinctional heterocyclic molecules. This reaction sequence takes place by either: a) an intramolecular oxy- or aminomercuration of an allene followed by a transmetallation of the mercury by palladium(II), then a coupling reaction (e.g., with carbon monoxide and an alcohol to form estCTs); or b) an intramolecular oxy- or aminopalladation of an allene followed, in situ, by the coupling. The results of this investigation have led to: 1) the development of a stereospecific approach to cis-2-15-alkyltetrahydrofiiran-2-yl)-2-propenoates; 2) the discovery of a stereospecific reduction of cis-2-(5-alkyltetrahydrofuran-2-yl)-2-propenoates; and 3) the development of a general synthetic approach to natural and unnatural nonactic acid esters. Scheme 1 represents our basic idea for the intramolecular nucleometallation of allenes (1) using mercury or palladium salts. A metal-complexed allene (2) should cyclize to form an intermediate a-vinyl complex of the metal (3). The complex 3 (where M = palladium) can undergo carbonylation and alkoxide coupling in the presence of carbon monoxide and an alcohol to form substituted acrylate esters (4) which should be valuable intermediates for organic synthesis. | |
| dc.format.mimetype | application/pdf | |
| dc.identifier.uri | http://hdl.handle.net/2346/20774 | en_US |
| dc.language.iso | eng | |
| dc.publisher | Texas Tech University | en_US |
| dc.rights.availability | Unrestricted. | |
| dc.subject | Organic compounds -- Synthesis | en_US |
| dc.subject | Palladium catalysts | en_US |
| dc.subject | Tetrahydrofuran -- Synthesis | en_US |
| dc.subject | Allene -- Synthesis | en_US |
| dc.title | Stereoselective syntheses of functionalized tetrahydrofurans via intramolecular oxymetallations of allenes and syntheses of methyl nonactate homologues | |
| dc.type | Dissertation |