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dc.contributor.advisorConnell, Brianen_US
dc.creatorKang, Junen_US
dc.date.accessioned2011-10-21T22:03:41Zen_US
dc.date.accessioned2011-10-25T14:38:24Z
dc.date.available2011-10-21T22:03:41Zen_US
dc.date.available2011-10-25T14:38:24Z
dc.date.created2011-08en_US
dc.date.issued2011-10-21en_US
dc.date.submittedAugust 2011en_US
dc.identifier.urihttp://hdl.handle.net/1969.1/ETD-TAMU-2011-08-77en_US
dc.description.abstractThe homoaldol reaction is one of the most powerful methods for the construction of C–C bonds as well as 1,4-oxygenated compounds yet this reaction remains in challenging tasks due to the instability of homoenolates which spontaneously cyclize to the cyclopropanolate. A regioselective catalytic homoaldol equivalent reaction of 3-bromo vinyl acetate with aldehydes under Cr(III)-Mn(0) redox condition was developed. This homoaldol equivalent reaction allows access to the 1,4-oxygenated compounds that are not possible by a conventional aldol process. Mild hydrolysis of the vinyl acetate and reduction of the homoaldol adducts generated diols and lactols in high yield (99%). Further manipulation including stereoselective epoxidation and cyclopropanation was achieved in an efficient manner. Furans, found in many natural products and utilized in drug discovery, have been well studied but current synthetic methods toward furans have some limitations in functional group tolerance, substrate scope, and low product yield in many cases. A highly efficient and catalytic cycloisomerization reaction that transforms acetylenic α,β-epoxides to 2,3,5-tri-substituted furans under InCl3 catalysis was developed. This reaction sequence allows access to rapid construction of highly valuable, tri-substituted furan derivatives. Cross-coupling reactions utilizing transition metals and Lewis acids are important synthetic tools for the formation of C–C and C–N bonds and a number of cross-coupling reactions between α-bromo carbonyl compounds and metal reagents such as aryl metals, alkenyl metals, and alkyl metals have been reported. Transition metal-catalyzed cross-coupling reaction for the construction of α-alkynyl carbonyl compounds has reported in a limited case. The first approach to secondary α-alkynyl carbonyl compounds from secondary α-bromo esters and amides with tributyl(phenylethynyl)stannane under palladium-catalyzed cross-coupling reaction conditions was developed. This synthetic method allows access to secondary α-alkynyl carbonyl compounds which are valuable precursors in pharmaceuticals and agricultural applications.en_US
dc.format.mimetypeapplication/pdfen_US
dc.language.isoen_USen_US
dc.subjecthomoaldol reactionen_US
dc.subjectChromiumen_US
dc.subjectCr(III)-Mn(0) redox conditionen_US
dc.subjecthomoenolatesen_US
dc.subject1,4-oxygenated compoundsen_US
dc.subjectdiolsen_US
dc.subjectlactolsen_US
dc.subjectstereoselective epoxidationen_US
dc.subjectstereoselective cyclopropanationen_US
dc.subjectFuransen_US
dc.subjectindiumen_US
dc.subjectacetylenic α,β-epoxidesen_US
dc.subjectcycloisomerizationen_US
dc.subjectpalladiumen_US
dc.subjectCross-coupling reactionsen_US
dc.subjectα-alkynyl carbonyl compoundsen_US
dc.titleChromium-Catalyzed Homoaldol Equivalent Reaction, Indium-Mediated Cycloisomerization, and Palladium-Catalyzed Cross-Coupling Reactionen_US
dc.typeThesisen
thesis.degree.departmentChemistryen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.grantorTexas A&M Universityen_US
thesis.degree.nameDoctor of Philosophyen_US
thesis.degree.levelDoctoralen_US
dc.contributor.committeeMemberBurgess, Kevinen_US
dc.contributor.committeeMemberShantz, Daniel; Romo, Danielen_US
dc.type.genrethesisen_US
dc.type.materialtexten_US


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