Development of Binaphthyl-Based Chiral Ligands for Dirhodium(II) Complexes, Studies toward the Total Synthesis of Carnosol, and Allylic Substitution of Silylenol Ethers

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dc.contributor.advisorMay, Jeremy A.
dc.contributor.committeeMemberThummel, Randolph P.
dc.contributor.committeeMemberDo, Loi H.
dc.contributor.committeeMemberTeets, Thomas S.
dc.contributor.committeeMemberCuny, Gregory D.
dc.creatorSetthakarn, Krit 1987-
dc.date.accessioned2018-11-30T16:03:26Z
dc.date.available2018-11-30T16:03:26Z
dc.date.createdMay 2018
dc.date.issued2018-05
dc.date.submittedMay 2018
dc.date.updated2018-11-30T16:03:26Z
dc.description.abstractThis dissertation presents three major projects. The first is the development of binaphthyl-based chiral ligands for dirhodium(II) complexes and their applications to enantioselective hydrazone-initiated carbene/alkyne cascade reactions. The second is the study toward the total synthesis of the natural product carnosol, using Rh(II)-catalyzed carbene/alkyne cascade reactions. The third is Brønsted acid-catalyzed allylic functionalization of silylenol ethers with organotrifluoroborates via oxyallyl cations. The synthesis and reactivities of a new chiral dirhodium(II) complex using chiral binaphthyl ligands, Rh2(R-KC4N)2, will be discussed herein. The structure of the new chiral rhodium(II) complex was based on Rh2(esp)2 and confirmed by single crystal X-ray diffraction. Reactivity studies with hydrazone initiated carbene/alkyne cascade reactions showed that the new chiral rhodium(II) complex can replicate or exceed the reactivity of Rh2(esp)2 in terms of product yields. Additionally, a second generation of rhodium(II) complexes based on Rh2(R-KC4N)2 has been designed, and its synthesis has been attempted. The second project relies on the use of a carbene/alkyne cascade reaction to construct bridged tricyclic molecules. The attempted synthesis of the core structure of carnosol implemented this carbene/alkyne cascade reaction using two key intermediates, a hydrazone and a diazo ketone. The third project explores a new strategy for functionalization of α-hydroxy silylenol ethers using organotrifluoroborate salts via oxyallyl cations. The preliminary studies showed that this new strategy provides promising results with broadened nucleophile scopes.
dc.description.departmentChemistry, Department of
dc.format.digitalOriginborn digital
dc.format.mimetypeapplication/pdf
dc.identifier.urihttp://hdl.handle.net/10657/3448
dc.language.isoeng
dc.rightsThe author of this work is the copyright owner. UH Libraries and the Texas Digital Library have their permission to store and provide access to this work. Further transmission, reproduction, or presentation of this work is prohibited except with permission of the author(s).
dc.subjectRhodium(II) complexes
dc.subjectCarbenes
dc.subjectCascade reactions
dc.subjectBINOL derivatives
dc.subjectChiral ligands
dc.subjectCarnosol
dc.subjectSilylenol ether
dc.subjectTrifluoroborate salt
dc.subjectAllylic substitution
dc.subjectOxyallyl cation
dc.titleDevelopment of Binaphthyl-Based Chiral Ligands for Dirhodium(II) Complexes, Studies toward the Total Synthesis of Carnosol, and Allylic Substitution of Silylenol Ethers
dc.type.dcmiText
dc.type.genreThesis
local.embargo.lift2020-05-01
local.embargo.terms2020-05-01
thesis.degree.collegeCollege of Natural Sciences and Mathematics
thesis.degree.departmentChemistry, Department of
thesis.degree.disciplineChemistry
thesis.degree.grantorUniversity of Houston
thesis.degree.levelDoctoral
thesis.degree.nameDoctor of Philosophy

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