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Reaction development and mechanistic investigation of rhodium-catalyzed pyridine synthesis via C-H activation

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dc.contributor.authorNeely, Jamie M., author
dc.contributor.authorRovis, Tomislav, advisor
dc.contributor.authorMcNally, Andrew, committee member
dc.contributor.authorFisk, John D., committee member
dc.contributor.authorNeilson, James R., committee member
dc.contributor.authorInamine, Julia M., committee member
dc.date.accessioned2007-01-03T05:57:30Z
dc.date.available2007-01-03T05:57:30Z
dc.date.issued2014
dc.description.abstractDescribed herein are two complementary rhodium-catalyzed methods for the synthesis of substituted pyridines from unsaturated oxime derivatives and alkenes. In the first, formal [4+2] cycloaddition of O-pivaloyl α, β-unsaturated oxime esters and activated terminal alkenes was discovered to proceed in high yields and with excellent selectivity for 6-substituted pyridine products. Mechanistic experiments were found to be consistent with a reversible C-H activation step and a C-N bond forming, N-O bond cleaving process en route to pyridine formation. Rhodium-catalyzed coupling using unactivated alkene substrates was shown to present important information regarding the influence of the alkene component on product distribution. In a second method, access to 5-substituted pyridine derivatives was achieved by decarboxylative annulation of α, β-unsaturated oxime esters and β-substituted acrylic acid derivatives. In this case, carboxylic acids were found to serve as traceless activating groups for selective alkene incorporation. A wealth of mechanistic insight was gained by identification of and decomposition studies regarding catalytically relevant rhodium complexes.
dc.format.mediumborn digital
dc.format.mediumdoctoral dissertations
dc.identifierNeely_colostate_0053A_12806.pdf
dc.identifier.urihttp://hdl.handle.net/10217/88453
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.subjectrhodium
dc.subjectoxime esters
dc.subjectpyridines
dc.subjectalkenes
dc.subjectC-H activation
dc.titleReaction development and mechanistic investigation of rhodium-catalyzed pyridine synthesis via C-H activation
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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