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dc.contributor.advisorHarmata, Michael, 1959-eng
dc.contributor.authorZheng, Pinguan, 1977-eng
dc.date.issued2007eng
dc.date.submitted2007 Falleng
dc.descriptionThe entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file.eng
dc.descriptionTitle from title screen of research.pdf file (viewed on March 4, 2008)eng
dc.descriptionVita.eng
dc.descriptionThesis (Ph. D.) University of Missouri-Columbia 2007.eng
dc.description.abstractDeantiaromatization has been successfully demonstrated as a driving force in an electrocyclization of cyclopentadienones. The reaction was found to be general for a number of substrates and provides a unique way to access tricyclic ring systems with high stereoselectivity. Some evidence was uncovered to show that the process is indeed an 8 [pi] conrotatory electrocyclic ring closure. During the exploration of substituent effects in the electrocyclization, a novel coupling reaction of an organolithium with primary halides was discovered. The experimental data suggested the engagement of the silicon atom and the important role of terminal alkene in the coupling reaction. However, the application of thiw methodology to other silane systems was successful. The total synthesis of 1-epi-seco-pseudopteroxazole was accomplished in 17 steps, featuring the Buchwald-Hartwig coupling, a stereoselective intramolecular Michael reaction, a Heck coupling and asymmetric reduction of trisubstituted alkene. In the course of reductive cleavage of the C-I bond to access key intermediate 358, a novel dephenylation of Harmata benzothiazines was discovered to provide chiral cyclic sulfinamides with complete stereocontrol. Preliminary mechanistic studies were carried out and a plausible mechanism was proposed based on our experimental results.eng
dc.description.bibrefIncludes bibliographical references.eng
dc.identifier.merlinb62412589eng
dc.identifier.oclc212783458eng
dc.identifier.urihttps://doi.org/10.32469/10355/4669eng
dc.identifier.urihttps://hdl.handle.net/10355/4669
dc.languageEnglisheng
dc.publisherUniversity of Missouri--Columbiaeng
dc.relation.ispartofcommunityUniversity of Missouri--Columbia. Graduate School. Theses and Dissertationseng
dc.rightsOpenAccess.eng
dc.rights.licenseThis work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivs 3.0 License.
dc.subjectcyclopentadienone; 1-epi-seco-pseudopteroxazole.eng
dc.subjectcyclopentadienone; 1-epi-seco-pseudopteroxazoleeng
dc.subject.lcshAromaticity (Chemistry)eng
dc.subject.lcshCharge transfereng
dc.subject.lcshRing formation (Chemistry)eng
dc.titleDeantiaromatization as a driving force in an electrocyclization of cyclopentadienone and the total synthesis of 1-epi-esco-pseudopteroxazoleeng
dc.typeThesiseng
thesis.degree.disciplineChemistry (MU)eng
thesis.degree.grantorUniversity of Missouri--Columbiaeng
thesis.degree.levelDoctoraleng
thesis.degree.namePh. D.eng


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