New Methods for the Formation of Methyl Bearing Stereogenic Centers via Methylketene Dimerization and Free Radical Additions to Allyl Bromides

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dc.contributor.authorStruss, John Anthonyen
dc.contributor.committeechairTanko, James M.en
dc.contributor.committeememberBrewer, Karen J.en
dc.contributor.committeememberCastagnoli, Neal Jr.en
dc.contributor.committeememberCarlier, Paul R.en
dc.contributor.committeememberDeck, Paul A.en
dc.contributor.departmentChemistryen
dc.date.accessioned2014-03-14T20:15:28Zen
dc.date.adate2002-09-12en
dc.date.available2014-03-14T20:15:28Zen
dc.date.issued2002-08-15en
dc.date.rdate2003-09-12en
dc.date.sdate2002-08-20en
dc.description.abstractTwo organic synthetic methods for the generation of methyl bearing chiral centers have been developed using: 1) dimerization of methylketene and 2) a free radical-based addition/elimination reaction involving allyl bromides. The first method, the asymmetric dimerization of methyl ketene, followed by an asymmetric aldol reaction and the appropriate functional group manipulations enabled us to construct the (2S, 4S, 6S) trimethylnonyl subunit found in the siphonariene class of natural products. The latter method explored the stereoselective potential of a free radical-based condensation reaction by examining compounds which are known to be able to support chiral auxiliaries and chiral Lewis acids. Additionally, substituent effect on the rates of this reaction were examined closely and found to be comparable to similar, previously examined systems. The synthetic utility, magnitude and scope of this reaction are discussed.en
dc.description.degreePh. D.en
dc.identifier.otheretd-08202002-151742en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-08202002-151742/en
dc.identifier.urihttp://hdl.handle.net/10919/28734en
dc.publisherVirginia Techen
dc.relation.haspartDissertation.pdfen
dc.relation.haspartTitleabstract.pdfen
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subjectAllyl Bromideen
dc.subjectMethylketeneen
dc.subjectAllyl Transferen
dc.subjectSiphonarienalen
dc.subjectAsymmetric Synthesisen
dc.subjectFree Radicalen
dc.titleNew Methods for the Formation of Methyl Bearing Stereogenic Centers via Methylketene Dimerization and Free Radical Additions to Allyl Bromidesen
dc.typeDissertationen
thesis.degree.disciplineChemistryen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.leveldoctoralen
thesis.degree.namePh. D.en

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