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

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dc.contributor.advisor Maguire, Anita R. en O'Neill, Shane T. en 2014-03-05T16:13:56Z 2012 2013
dc.identifier.citation O'Neill, S. T. 2012. Catalyst, additive and substrate effects in intramolecular aromatic additions of alpha-diazoketones. PhD Thesis, University College Cork. en
dc.identifier.endpage 304
dc.description.abstract This 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.sponsorship Irish Research Council for Science Engineering and Technology (EMBARK initiative) en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher University College Cork en
dc.rights © 2012, Shane T. O'Neill. en
dc.rights.uri en
dc.subject Asymmetric catalysis en
dc.subject Diazoketones en
dc.subject Buchner reaction en
dc.subject Additive effect en
dc.subject Ligand en
dc.subject.lcsh Asymmetric synthesis en
dc.subject.lcsh Catalysis en
dc.title Catalyst, additive and substrate effects in intramolecular aromatic additions of alpha-diazoketones en
dc.title.alternative Catalyst, additive and substrate effects in intramolecular aromatic additions of α-diazoketones en
dc.type Doctoral thesis en
dc.type.qualificationlevel Doctoral Degree (Structured) en
dc.type.qualificationname PhD (Science) en
dc.internal.availability Full text available en
dc.description.version Accepted Version
dc.contributor.funder Irish Research Council for Science Engineering and Technology en
dc.description.status Not peer reviewed en Chemistry en
dc.check.reason This thesis is due for publication or the author is actively seeking to publish this material en
dc.check.opt-out Not applicable en
dc.thesis.opt-out false
dc.check.embargoformat E-thesis on CORA only en
dc.internal.conferring Autumn Conferring 2013 en

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© 2012, Shane T. O'Neill. Except where otherwise noted, this item's license is described as © 2012, Shane T. O'Neill.
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