dc.contributor.advisor | Harmata, Michael, 1959- | eng |
dc.contributor.author | Zheng, Pinguan, 1977- | eng |
dc.date.issued | 2007 | eng |
dc.date.submitted | 2007 Fall | eng |
dc.description | The 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.description | Title from title screen of research.pdf file (viewed on March 4, 2008) | eng |
dc.description | Vita. | eng |
dc.description | Thesis (Ph. D.) University of Missouri-Columbia 2007. | eng |
dc.description.abstract | Deantiaromatization 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.bibref | Includes bibliographical references. | eng |
dc.identifier.merlin | b62412589 | eng |
dc.identifier.oclc | 212783458 | eng |
dc.identifier.uri | https://doi.org/10.32469/10355/4669 | eng |
dc.identifier.uri | https://hdl.handle.net/10355/4669 | |
dc.language | English | eng |
dc.publisher | University of Missouri--Columbia | eng |
dc.relation.ispartofcommunity | University of Missouri--Columbia. Graduate School. Theses and Dissertations | eng |
dc.rights | OpenAccess. | eng |
dc.rights.license | This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivs 3.0 License. | |
dc.subject | cyclopentadienone; 1-epi-seco-pseudopteroxazole. | eng |
dc.subject | cyclopentadienone; 1-epi-seco-pseudopteroxazole | eng |
dc.subject.lcsh | Aromaticity (Chemistry) | eng |
dc.subject.lcsh | Charge transfer | eng |
dc.subject.lcsh | Ring formation (Chemistry) | eng |
dc.title | Deantiaromatization as a driving force in an electrocyclization of cyclopentadienone and the total synthesis of 1-epi-esco-pseudopteroxazole | eng |
dc.type | Thesis | eng |
thesis.degree.discipline | Chemistry (MU) | eng |
thesis.degree.grantor | University of Missouri--Columbia | eng |
thesis.degree.level | Doctoral | eng |
thesis.degree.name | Ph. D. | eng |