Synthetic and stereochemical aspects of intramolecular reactions of α-diazoketones catalysed by rhodium(II) carboxylates

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dc.contributor.advisor McKervey, M. A. en
dc.contributor.author Maguire, Anita R.
dc.date.accessioned 2014-09-16T09:29:29Z
dc.date.available 2014-09-16T09:29:29Z
dc.date.issued 1989
dc.date.submitted 1989
dc.identifier.citation Maguire, A. R. 1989. Synthetic and stereochemical aspects of intramolecular reactions of α-diazoketones catalysed by rhodium(II) carboxylates. PhD Thesis, University College Cork. en
dc.identifier.uri http://hdl.handle.net/10468/1664
dc.description.abstract Chapter 1 of this thesis is a brief introduction to the preparation and reactions of α-diazocarbonyl compounds, with particular emphasis on the areas relating to the research undertaken: C-H insertion, addition to aromatics, and oxonium ylide generation and rearrangement. A short summary of catalyst development illustrates the importance of rhodium(II)carboxylates for α-diazocarbonyl decomposition. Chapter 2 describes intramolecular C-H insertion reactions of α-diazo-β-keto sulphones to form substituted cyclopentanones. Rhodium(II) carboxylates derived from homochiral carboxylic acids were used as catalysts in these reactions and enantioselection achieved through their use is discussed. Chapter 3 describes intramolecular Buchner cyclisation of aryl diazoketones with emphasis on the stereochemical aspects of the cyclisation and subsequent reaction of the bicyclo[5.3.0]decatrienones produced. The partial asymmetric synthesis achieved through use of chiral rhodium(II) carboxylates as catalysts is discussed. The application of the intramolecular Buchner reaction to the synthesis of hydroazulene lactones is illustrated. Chapter 4 demonstrates oxonium ylide formation and rearrangement in the decomposition of an α-diazoketone. The consequences of the use of chiral rhodium(II) carboxylates as catalysts are described. Particularly significant was the discovery that rhodium(II) (S)-mandelate acts as a very efficient catalyst for α-diazoketone decompositions, in general. Moderate asymmetric induction was possible in the decomposition of α-diazoketones with chiral rhodium(II) carboxylates, with rhodium(II) (S)-mandelate being one of the more enantioselective catalysts investigated. However, the asymmetric induction obtained was very dependent on the exact structure of the α-diazoketone, the catalyst, and the nature of the reaction. Chapter 5 contains the experimental details, and the spectral and analytical data for all new compounds reported. en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher University College Cork en
dc.relation.uri http://library.ucc.ie/record=b1159687~S0
dc.rights © 1989, Anita R. Maguire en
dc.rights.uri http://creativecommons.org/licenses/by-nc-nd/3.0/ en
dc.subject α-diazoketones en
dc.subject Rhodium(II) carboxylates en
dc.subject Intramolecular reactions en
dc.subject.lcsh Chemistry, Organic en
dc.title Synthetic and stereochemical aspects of intramolecular reactions of α-diazoketones catalysed by rhodium(II) carboxylates en
dc.type Doctoral thesis en
dc.type.qualificationlevel Doctoral en
dc.type.qualificationname PhD (Science) en
dc.internal.availability Full text available en
dc.check.info No embargo required en
dc.description.version Accepted Version
dc.contributor.funder Department of Education, Ireland en
dc.contributor.funder GlaxoSmithKline, United Kingdom en
dc.contributor.funder Cork County Council en
dc.description.status Not peer reviewed en
dc.internal.school Chemistry en
dc.check.type No Embargo Required
dc.check.reason No embargo required en
dc.check.opt-out Not applicable en
dc.thesis.opt-out false
dc.check.embargoformat Not applicable en
ucc.workflow.supervisor cora@ucc.ie


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© 1989, Anita R. Maguire Except where otherwise noted, this item's license is described as © 1989, Anita R. Maguire
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