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dc.contributor.advisorDutta, Apurba
dc.contributor.authorVekariya, Rakesh H.
dc.date.accessioned2016-10-11T18:45:25Z
dc.date.available2016-10-11T18:45:25Z
dc.date.issued2016-08-31
dc.date.submitted2016
dc.identifier.otherhttp://dissertations.umi.com/ku:14828
dc.identifier.urihttp://hdl.handle.net/1808/21652
dc.description.abstractCycloaddition of allylic azides and alkynes. The 1,3-dipolar Huisgen azide-alkyne cycloaddition is a significant area of interest in modern chemistry. The use of allylic azides as dynamic reaction partners represent a novel variant of this chemistry as they undergo facile 1,3-allylic azide rearrangement, which is also known as the Winstein rearrangement. We combined such an allylic azide rearrangement with an intramolecular Huisgen cycloaddition to afford substituted triazoles in a diastereoselective fashion. Although modest diastereoselectivity was observed in most cases, the majority of diastereomeric pairs were separable. Also, depending on the conditions, a difference in the reactivity of various allylic azides was noticed. Under thermal conditions, vinyl-substituted triazoloxazines were formed, in contrast to copper(I)-catalyzed conditions which afforded dimerized macrocyclic products. Hexafluoro-2-propanol promoted Friedel–Crafts acylation reactions. The Friedel–Crafts acylation is one of the most important reactions in both academia and industry for the synthesis of aromatic ketones. The reaction is typically promoted by stoichiometric or greater amounts of acids, such as AlCl3, FeCl3, or H2SO4, which activate the carbonyl for attack by an aromatic group. A drawback of this extremely versatile acylation reaction is the generation of large amounts of corrosive aqueous waste following post-synthesis workup. We have shown that hexafluoro-2-propanol (HFIP) promotes both intramolecular and intermolecular FC acylation without additional catalysts or reagents. This solvent-promoted acylation is practically simple and accommodates a broad substrates scope. Our preliminary kinetic studies reflects involvement of 3 molecules of HFIP in rate determing step.
dc.format.extent223 pages
dc.language.isoen
dc.publisherUniversity of Kansas
dc.rightsCopyright held by the author.
dc.subjectPharmaceutical sciences
dc.subjectOrganic chemistry
dc.subjectChemistry
dc.subjectallylic azide rearrangement
dc.subjectazide-alkyne cycloaddition
dc.subjectcopper(I)-catalyzed azide-alkyne cycloaddition
dc.subjectFriedel–Crafts acylation
dc.subjecthexafluoro-2-propanol
dc.subjectHFIP
dc.titleStudies and Synthetic Methodology: 1. Cycloaddition of Allylic Azides and Alkynes, 2. Hexafluoro-2-propanol-promoted Friedel–Crafts Acylation Reactions
dc.typeDissertation
dc.contributor.cmtememberAubé, Jeffrey
dc.contributor.cmtememberBlagg, Brian
dc.contributor.cmtememberPrisinzano, Thomas
dc.contributor.cmtememberHanson, Paul R
dc.thesis.degreeDisciplineMedicinal Chemistry
dc.thesis.degreeLevelPh.D.
dc.identifier.orcid
dc.identifier.orcidhttps://orcid.org/0000-0001-8292-9793
dc.provenance04/05/2017: The ETD release form is attached to this record as a license file.
dc.rights.accessrightsopenAccess


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