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dc.contributor.authorBui, Binh H
dc.date.accessioned2014-03-04T01:08:16Z
dc.date.available2014-03-04T01:08:16Z
dc.date.issued2006-08
dc.identifier.otherbui_binh_h_200608_ms
dc.identifier.urihttp://purl.galileo.usg.edu/uga_etd/bui_binh_h_200608_ms
dc.identifier.urihttp://hdl.handle.net/10724/23323
dc.description.abstractIn predicting new reactions, systematic strategies involving the classification of systems of interest and methodological applications of computational tools are used to study heterosubstituted polyunsaturated hydrocarbons. Although this is a rather “heuristic approach,” it provides qualitatively reasonable results and collective findings of reaction families. A systematic application of the BLYP/6-311+G*//BLYP/6-31G* computational scheme was utilized to study the thermal rearrangements of 4-heteroatom-1,2-hexadiene-5-ynes (Chapter 2), 3-heteroatom-pent-1-en-4-yn-1-ones (Chapter 3), and (hetero)atom-bridged diallenes (Chapter 4). It was found that the aromatization 2,6-cyclization path leading to the formally aromatic five-membered ring products are preferred and experimentally accessible. Protonation of the heteroatom X resulted in either the 1,6-Claisen-type rearrangement to form the stable acyclic product or the competitive 1,6-cyclization mode to form homoaromatic six-membered ring products. The Ã-electron-withdrawing and À-electron-donating abilities of the heteroatom (or group) X have been determined to be effective in governing the reaction barriers (TS26) but not the reaction energies.
dc.languageeng
dc.publisheruga
dc.rightspublic
dc.subjectenyne-allenes
dc.subjectenyne-ketenes
dc.subjectdiallenes
dc.subjectenones
dc.subjectenynes
dc.subjectradicals
dc.subjectreaction family
dc.subjectheterosubstituted polyunsaturated hydrocarbons
dc.subjectrearrangements
dc.titleThermal rearrangements of heteroatom-bridged polyunsaturated hydrocarbons
dc.typeThesis
dc.description.degreeMS
dc.description.departmentChemistry
dc.description.majorChemistry
dc.description.advisorGeorge Majetich
dc.description.committeeGeorge Majetich
dc.description.committeeRobert S. Phillips
dc.description.committeeTimothy M. Dore


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