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dc.contributor.authorVaccarello, David Nicholas
dc.date.accessioned2018-04-26T14:15:41Z
dc.date.available2019-09-11T06:02:25Z
dc.date.issued2017-08-30
dc.identifier.otherVaccarello_cornellgrad_0058F_10361
dc.identifier.otherhttp://dissertations.umi.com/cornellgrad:10361
dc.identifier.otherbibid: 10361399
dc.identifier.urihttps://hdl.handle.net/1813/56722
dc.description.abstractMy doctoral studies have concentrated on the use of C2-symmetic catalysts to control the three-dimensional construction of molecules. The first half of my thesis focuses on asymmetric addition of phenols into Pd π-allyl complexes. This work was inspired by the natural product, sch202596, an antagonist for the galinin receptor that contains a highly stereogenic and compact carbasurgar structure appended onto a phenol by an allylic aryl-ether bond. A transformation was developed in which racemic allylic oxides underwent a Tsuji-Trost reaction to give diastereomeric π-allyl complexes. Addition of a nucleophile resulted in enantioenriched regioisomers in good yields. We termed this approach allylic oxide regio resolution (AORR). Using this approach, four different carbasurgar natural products were synthesized: streptol, MK7607, cyathiformine B and polyporapyranone G. Additionally, this method was extended to append carbasugar-like molecules onto complex natural products. Furthermore, C2-symmetic catalysts were used to synthesize polymers with stereoregularity, which will be the focus of the second half of my thesis. Utilizing advances in chain walking polymerization, 1-butene was polymerized resulting in a novel isotactic semi-crystalline polymer. The ligand framework and reaction conditions were probed in order to optimized the system, which gave an active catalyst that produced a polymer with few stereo and regioerros. Specifically, it was found that ortho-cumyl groups were necessary to maintain the stereochemical information through the chain walking steps. Additionally reaction conditions were explored and discovered that a reaction temperature of −40 °C and a concentration of approximately 8 M were the optimal conditions. Finally, the use of non-aromatic, high polarity, aprotic solvents proved beneficial.
dc.language.isoen_US
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 International*
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.subjectMaterials Science
dc.subjectbutene
dc.subjectcarbasugar
dc.subjectsynthesis
dc.subjectPolymer chemistry
dc.subjectPolymer
dc.subjectOrganic chemistry
dc.titleCONTROLLING ARCHITECTURE USING C2-SYMMETRIC CATALYSTS: FROM SMALL MOLECULES TO LARGE POLYMERS
dc.typedissertation or thesis
thesis.degree.disciplineChemistry and Chemical Biology
thesis.degree.grantorCornell University
thesis.degree.levelDoctor of Philosophy
thesis.degree.namePh. D., Chemistry and Chemical Biology
dc.contributor.chairCoates, Geoffrey
dc.contributor.committeeMemberLancaster, Kyle M.
dc.contributor.committeeMemberCollum, David B.
dcterms.licensehttps://hdl.handle.net/1813/59810
dc.identifier.doihttps://doi.org/10.7298/X4F18WW3


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