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dc.contributor.advisorJacobsen, Eric N.
dc.contributor.authorMayfield, Andrew Beckmann
dc.date.accessioned2019-08-08T09:24:17Z
dash.embargo.terms2021-03-01
dc.date.created2019-03
dc.date.issued2019-01-20
dc.date.submitted2019
dc.identifier.citationMayfield, Andrew Beckmann. 2019. Multifunctional Hydrogen-Bond-Donor Catalysts for Selective Furanosylation. Doctoral dissertation, Harvard University, Graduate School of Arts & Sciences.
dc.identifier.urihttp://nrs.harvard.edu/urn-3:HUL.InstRepos:41121310*
dc.description.abstractHydrogen-bond-donor catalysts are applied to the construction of challenging 1,2-cis glycosidic linkages of arabinose and other furanose sugars. Identification of an unusual dialkylphosphate leaving group enables preparation of anomerically-pure furanoside substrates suitable for use in a stereospecific glycosylation method. Based on previous glycosylation studies performed in the Jacobsen lab, we propose that hydrogen-bond-donor catalysts promote stereospecificity through concomitant nucleophile- and electrophile-activation. This stereospecific glycosylation method enables synthetic access to diverse furanose linkages in high anomeric ratios. Catalyst-promoted anomerization of the substrate is identified as a major factor leading to the formation of the undesired minor glycoside product. Multifunctional activation in hydrogen-bond-donor catalysis is further examined from a fundamental perspective in transesterification reactions promoted by trifunctional ureas designed to mimic mechanistic features of serine proteases. The importance of the hydrogen-bond donor to catalytic activity in these reactions is quantified, and the mechanistic role of the hydrogen-bond-donor is evaluated.
dc.description.sponsorshipChemistry and Chemical Biology
dc.format.mimetypeapplication/pdf
dc.language.isoen
dash.licenseLAA
dc.subjectOrganocatalysis
dc.subjectGlycosylation
dc.subjectFuranoses
dc.subjectHydrogen-Bond-Donors
dc.titleMultifunctional Hydrogen-Bond-Donor Catalysts for Selective Furanosylation
dc.typeThesis or Dissertation
dash.depositing.authorMayfield, Andrew Beckmann
dash.embargo.until2021-03-01
dc.date.available2019-08-08T09:24:17Z
thesis.degree.date2019
thesis.degree.grantorGraduate School of Arts & Sciences
thesis.degree.grantorGraduate School of Arts & Sciences
thesis.degree.levelDoctoral
thesis.degree.levelDoctoral
thesis.degree.nameDoctor of Philosophy
thesis.degree.nameDoctor of Philosophy
dc.contributor.committeeMemberBalskus, Emily P.
dc.contributor.committeeMemberBetley, Theodore A.
dc.type.materialtext
thesis.degree.departmentChemistry and Chemical Biology
thesis.degree.departmentChemistry and Chemical Biology
dash.identifier.vireo
dash.author.emailorganicoboist@gmail.com


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