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dc.contributor.advisorClarke, Matt
dc.contributor.authorDurrani, Jamie T.
dc.description.abstractPalladium catalysed asymmetric hydroxy- and alkoxycarbonylation reactions of alkenes have the potential to deliver valuable chiral carboxylic acid and ester building blocks from cheap feedstocks: alkenes, carbon monoxide and water (alcohols in the case of alkoxycarbonylation). Despite the attractive nature of these reactions, extensive research has so far been unable to produce effective catalysts which are capable of controlling both regio- and enantioselectivity. Building on exciting recent results involving the use of highly enantioselective palladium catalysts derived from Phanephos-type ligands, this research focuses on paracyclophane-diphosphines and their use in asymmetric hydroxy- and alkoxycarbonylation reactions. An investigation into reaction conditions analysed several factors, including solvents, CO-pressure, acidic additives and halide sources, to provide optimal activity and selectivities. Two novel electron-poor paracyclophane-diphosphines and their mono- and di-palladium complexes were synthesised and shown to provide exceptional levels of regioselectivity while maintaining high levels of asymmetric induction. These are the first such examples of hydroxy- or alkoxycarbonylation catalysts to facilitate simultaneous control over both regio- and enantioselectivity. The most effective catalyst was used to promote the reactions of a selection of aryl alkenes and was shown to be tolerant of several different functional groups. A selection of non-symmetric paracyclophane-diphosphine ligands and their palladium complexes were also synthesised and assessed for their performance in hydroxy- and alkoxycarbonylation. We also report the use of Phanephos-type ligands to promote the highly enantioselective hydroxycarbonylation of N-(p-toluenesulfonyl)-3-pyrroline to deliver a chiral proline derivative in high ee.en_US
dc.publisherUniversity of St Andrews
dc.subjectAsymmetric catalysisen_US
dc.subjectHomogeneous catalysisen_US
dc.subject.lcshCarbonyl compounds--Synthesisen_US
dc.subject.lcshPalladium catalystsen_US
dc.subject.lcshHomogeneous catalysisen_US
dc.subject.lcshAsymmetry (Chemistry)en_US
dc.titlePalladium catalysed asymmetric hydroxy- and alkoxycarbonylation of alkenesen_US
dc.contributor.sponsorDr. Reddy's Chirotech Technology Ltd.en_US
dc.contributor.sponsorEngineering and Physical Sciences Research Council (EPSRC)en_US
dc.type.qualificationnamePhD Doctor of Philosophyen_US
dc.publisher.institutionThe University of St Andrewsen_US
dc.rights.embargoreasonThesis restricted in accordance with University regulations. Print and electronic copy restricted until 4th February 2021en_US

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