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dc.contributor.advisorLam, Hon
dc.contributor.advisorLusby, Paul
dc.contributor.authorFallan, Charlene
dc.date.accessioned2013-08-14T15:17:39Z
dc.date.available2013-08-14T15:17:39Z
dc.date.issued2012-11-28
dc.identifier.urihttp://hdl.handle.net/1842/7683
dc.description.abstractI. Catalytic Conjugate Allylation of Alkylidene Malonates Nucleophilic conjugate addition of allylsilanes and allylstannanes to alkylidene malonates under the action of ytterbium catalysis in the presence of hexafluoro-isopropanol has been developed. Enantioselective conjugate allylation of alkylidene malonates under ytterbium or scandium catalysis using chiral bis(oxazoline) ligands allows access to the conjugate addition products in an enantiomerically-enriched form. Furthermore, elaboration of the allylated substrates via decarboxylation and an oxidative cleavage was demonstrated. II. Catalytic Enantioselective Conjugate Addition of Azaarylacetates and Acetamides to Nitroalkenes An enantioselective nickel-catalysed Michael addition of azaarylacetates and acetamides to nitroalkenes has been developed. A range of azaaryl pronucleophiles were shown to react with a variety of nitroalkenes to generate highly functionalised Michael addition products with impressive diastereo- and enantiocontrol. A possible mechanism for this process is proposed and crystal structures of the addition products have also been attained, allowing determination of the absolute stereochemistry. Elaboration and further functionalisation of these products was also possible under a range of conditions.en_US
dc.contributor.sponsorScottish Funding Councilen_US
dc.language.isoenen_US
dc.publisherThe University of Edinburghen_US
dc.relation.hasversionYtterbium-Catalyzed Conjugate Allylation of Alkylidene Malonates, Fallan, C.; Quigley, P. F.; Lam, H. W. J. Org. Chem. 2011, 76, 4112−4118.en_US
dc.relation.hasversionEnantioselective Nickel-Catalyzed Michael Additions of Azaarylacetates and Acetamides to Nitroalkenes, Fallan, C.; Lam, H. W.; Chem. Eur. J. 2012, Chem. Eur. J. 2012, 18, 11214 – 11218.en_US
dc.subjectorganic chemistryen_US
dc.subjectasymmetric catalysisen_US
dc.titleYtterbium-catalysed conjugate allylation of alkylidene malonates and enantioselective nickel-catalysed Michael additions of azaarylacetates and acetamides to nitroalkenesen_US
dc.title.alternativeEnantioselective nickel-catalysed Michael additions of azaarylacetates and acetamides to nitroalkenesen_US
dc.typeThesis or Dissertationen_US
dc.type.qualificationlevelDoctoralen_US
dc.type.qualificationnamePhD Doctor of Philosophyen_US


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