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dc.contributor.advisorKrische, Michael J.en
dc.creatorCauble, David Fredericen
dc.date.accessioned2008-08-28T22:35:24Zen
dc.date.available2008-08-28T22:35:24Zen
dc.date.issued2004en
dc.identifierb60834705en
dc.identifier.urihttp://hdl.handle.net/2152/2155en
dc.descriptiontexten
dc.description.abstractTransition metal-catalyzed carbon-carbon bond-forming reactions are attractive methodological targets, as they enable the rapid build-up of molecular complexity. Herein is described research directed toward the development of highly practical, efficient and selective transition metal-catalyzed processes that facilitate the succinct, sequential formation of multiple chemical bonds: i. Catalysts derived from rhodium and copper are featured in tandem conjugate addition-electrophilic trapping reactions (tandem vicinal difunctionalization), leading to products of formal aldol, Dieckmann and Blaise cyclizations. In this context, the use of diastereotopic 1,3-dione electrophilic acceptors is examined. ii. Related rhodium catalysts are employed successfully in the catalytic reductive arylation of 1,3-cyclohexadiene. iii. The classical Gilman reagent (dimethyllithium cuprate-lithium iodide) is shown to catalyze the [2+2]cycloaddition of bis(enone) substrates in high yield. Effective partitioning between the 1,4-addition and cycloaddition manifolds is showcased and discussed. Finally, a strategy for the enantioselective catalysis of photo-mediated reactions in solution is described, involving the use of chiral molecular receptors possessing appendant triplet sensitizing moieties. Energy transfer is selectively directed to bound substrate as a consequence of the distance dependence of triplet-triplet energy transfer. This effect, which is equivalent to a binding induced rate enhancement, enables substoichiometric chirality transfer from the receptor template to the substrate, as observed in the intramolecular enone-olefin photo[2+2]cycloaddition of a quinolone substrate.
dc.format.mediumelectronicen
dc.language.isoengen
dc.rightsCopyright 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.lcshOrganic compounds--Synthesisen
dc.subject.lcshRing formation (Chemistry)en
dc.titleTransition metal and organo-catalyzed cyclizations, cycloadditions and couplingsen
dc.description.departmentChemistry and Biochemistryen
dc.description.departmentChemistryen
dc.identifier.oclc68963740en
dc.identifier.proqst3150558en
dc.type.genreThesisen
thesis.degree.departmentChemistryen
thesis.degree.disciplineChemistryen
thesis.degree.grantorThe University of Texas at Austinen
thesis.degree.levelDoctoralen
thesis.degree.nameDoctor of Philosophyen


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