Catalyst, additive and substrate effects in intramolecular aromatic additions of alpha-diazoketones

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dc.check.embargoformatE-thesis on CORA onlyen
dc.check.opt-outNot applicableen
dc.check.reasonThis thesis is due for publication or the author is actively seeking to publish this materialen
dc.contributor.advisorMaguire, Anita R.en
dc.contributor.authorO'Neill, Shane T.en
dc.contributor.funderIrish Research Council for Science Engineering and Technologyen
dc.date.accessioned2014-03-05T16:13:56Z
dc.date.issued2012
dc.date.submitted2013
dc.description.abstractThis thesis is focused on transition metal catalysed reaction of α-diazoketones leading to aromatic addition to form azulenones, with particular emphasis on enantiocontrol through use of chiral copper catalysts. The first chapter provides an overview of the influence of variation of the substituent at the diazo carbon on the outcome of subsequent reaction pathways, focusing in particular on C-H insertion, cyclopropanation, aromatic addition and ylide formation drawing together for the first time input from a range of primary reports. Chapter two describes the synthesis of a range of novel α-diazoketones. Rhodium and copper catalysed cyclisation of these to form a range of azulenones is described. Variation of the transition metal catalyst was undertaken using both copper and rhodium based systems and ligand variation, including the design and synthesis of a novel bisoxazoline ligand. The influence of additives, especially NaBARF, on the enantiocontrol was explored in detail and displayed an interesting impact which was sensitive to substituent effects. Further exploration demonstrated that it is the sodium cation which is critical in the additive effects. For the first time, enantiocontrol in the aromatic addition of terminal diazoketones was demonstrated indicating enantiofacial control in the aromatic addition is feasible in the absence of a bridgehead substituent. Determination of the enantiopurity in these compounds was particularly challenging due to the lability of the products. A substantial portion of the work was focused on determining the stereochemical outcome of the aromatic addition processes, both the absolute stereochemistry and extent of enantiopurity. Formation of PTAD adducts was beneficial in this regard. The third chapter contains the full experimental details and spectral characterisation of all novel compounds synthesised in this project, while details of chiral stationary phase HPLC and 1H NMR analysis are included in the appendix.en
dc.description.sponsorshipIrish Research Council for Science Engineering and Technology (EMBARK initiative)en
dc.description.statusNot peer revieweden
dc.description.versionAccepted Version
dc.format.mimetypeapplication/pdfen
dc.identifier.citationO'Neill, S. T. 2012. Catalyst, additive and substrate effects in intramolecular aromatic additions of alpha-diazoketones. PhD Thesis, University College Cork.en
dc.identifier.endpage304
dc.identifier.urihttps://hdl.handle.net/10468/1428
dc.language.isoenen
dc.publisherUniversity College Corken
dc.rights© 2012, Shane T. O'Neill.en
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/3.0/en
dc.subjectAsymmetric catalysisen
dc.subjectDiazoketonesen
dc.subjectBuchner reactionen
dc.subjectAdditive effecten
dc.subjectLiganden
dc.subject.lcshAsymmetric synthesisen
dc.subject.lcshCatalysisen
dc.thesis.opt-outfalse
dc.titleCatalyst, additive and substrate effects in intramolecular aromatic additions of alpha-diazoketonesen
dc.title.alternativeCatalyst, additive and substrate effects in intramolecular aromatic additions of α-diazoketonesen
dc.typeDoctoral thesisen
dc.type.qualificationlevelDoctoral Degree (Structured)en
dc.type.qualificationnamePhD (Science)en
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