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Organocatalytic, Michael-Stetter reaction and rhodium(I)-catalyzed hydroheteroarylation of acrylates with benzoxazoles: reaction development and investigations into origins of enantioselectivity

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dc.contributor.authorFilloux, Claire M., author
dc.contributor.authorRovis, Tomislav, advisor
dc.contributor.authorMcNaughton, Brian R., committee member
dc.contributor.authorPrieto, Amy L., committee member
dc.contributor.authorCrans, Debbie C., committee member
dc.contributor.authorHentges, Shane T., committee member
dc.date.accessioned2015-08-27T03:57:00Z
dc.date.available2015-08-27T03:57:00Z
dc.date.issued2015
dc.description.abstractThe chapters that follow describe two independent investigations. Both relay the development of experimental methods for the catalytic, asymmetric addition of carbon-hydrogen bonds to alkenes. In the first chapter, nucleophilic amine and N-heterocyclic carbene cocatalysts cooperate in the organocatalytic, cascade synthesis of benzofuranone products in good yields and high enantioselectivities. Importantly, the cascade protocol is found to outperform a two-pot procedure in which reaction intermediates are isolated and purified before the second step. Mechanistic studies reveal that additives and geometry of an olefin intermediate crucially influence reaction enantioselectivity. In the second method, a bulky Rh(I)-bisphosphine complex catalyzes the asymmetric, intermolecular addition of benzoxazoles to methacrylate derivatives in fair to excellent yields and good to excellent enantioselectivities. Detailed deuterium labeling and epimerization studies provide considerable insight into the reaction mechanism: C-H activation is reversible; migratory insertion is likely enantiodetermining; and the bulky- bisphosphine ligand likely boosts reactivity and selectivity by discouraging deleterious ligation of benzoxazole starting materials to on- or off-cycle rhodium complexes and by impeding coordination-induced product epimerization.
dc.format.mediumborn digital
dc.format.mediumdoctoral dissertations
dc.identifierFilloux_colostate_0053A_12865.pdf
dc.identifier.urihttp://hdl.handle.net/10217/166906
dc.languageEnglish
dc.language.isoeng
dc.publisherColorado State University. Libraries
dc.relation.ispartof2000-2019
dc.rightsCopyright and other restrictions may apply. User is responsible for compliance with all applicable laws. For information about copyright law, please see https://libguides.colostate.edu/copyright.
dc.subjectcatalysis
dc.subjectorganic
dc.subjectasymmetric
dc.subjectrhodium
dc.subjectN-heterocyclic carbene
dc.titleOrganocatalytic, Michael-Stetter reaction and rhodium(I)-catalyzed hydroheteroarylation of acrylates with benzoxazoles: reaction development and investigations into origins of enantioselectivity
dc.typeText
dcterms.rights.dplaThis Item is protected by copyright and/or related rights (https://rightsstatements.org/vocab/InC/1.0/). You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s).
thesis.degree.disciplineChemistry
thesis.degree.grantorColorado State University
thesis.degree.levelDoctoral
thesis.degree.nameDoctor of Philosophy (Ph.D.)

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