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dc.contributor.advisorKamer, Paul (Paul C. J.)
dc.contributor.authorGillespie, Jason A.
dc.coverage.spatial453en_US
dc.date.accessioned2012-09-20T20:34:11Z
dc.date.available2012-09-20T20:34:11Z
dc.date.issued2012-06
dc.identifieruk.bl.ethos.556393
dc.identifier.urihttps://hdl.handle.net/10023/3100
dc.description.abstractBy examining structure activity relationships for a given catalytic reaction it is possible to discover what ligand features and parameters lead to stable and highly active/selective catalyst systems. With this knowledge in hand it may be possible to rationally design next generation ligands and catalysts to affect improved substrate transformations, with higher selectivities and faster reaction times. The success of Burk’s DuPhos ligands in asymmetric hydrogenation demonstrated that chiral phosphacycles can be a potent source of chiral induction, whilst in a similar vein the work of van Leeuwen and Kamer established the wide bite angle xanthene based ligands as excellent catalysts in a range of reactions including hydroformylation. In a preliminary study with Osborne they showed that combining these wide bite angle ligand backbones with Burk’s phospholane moieties led to a new powerful ligand in asymmetric allylic substitution. To examine the potential of combining these two ligand features further we designed and synthesised nine new C2-symmetric bidentate wide bite angle bisphosphacyclic ligands, featuring phosphetane, phospholane or diazaphospholane rings, aiming at a wide diversity of steric and electronic properties. The application of these ligands as chiral auxiliaries in transition metal catalysed reactions, including; hydrogenation, hydrocyanation, hydroformylation and allylic alkylation has been investigated. Good to excellent enantioselectivities were observed in all reactions, with maximum ee’s of 92.5% observed in hydrogenation, using N-(3,4-dihydro-1-napthalenyl)-acetamide as substrate, and of 96.2% in the alkylation of 1,3-diphenyl-2-propenyl acetate.en_US
dc.language.isoenen_US
dc.publisherUniversity of St Andrews
dc.subjectAsymmetricen_US
dc.subjectCatalysisen_US
dc.subjectBidentateen_US
dc.subjectPhosphacycleen_US
dc.subjectPhospholaneen_US
dc.subjectPhosphetaneen_US
dc.subjectXantheneen_US
dc.subjectChiralen_US
dc.subjectHydrogenationen_US
dc.subjectAllylic substitutionen_US
dc.subjectHydroformylationen_US
dc.subjectHydrocyanationen_US
dc.subjectDiazaphospholaneen_US
dc.subjectC2 symmetricen_US
dc.subjectLiganden_US
dc.subjectTransition metalen_US
dc.subjectPalladiumen_US
dc.subjectRhodiumen_US
dc.subjectNickleen_US
dc.subject.lccQD474.G5
dc.subject.lcshLigands--Synthesisen_US
dc.subject.lcshCatalysts--Synthesisen_US
dc.subject.lcshTransition metal catalystsen_US
dc.titleDesign and synthesis of wide bite angle phosphacyclic ligandsen_US
dc.typeThesisen_US
dc.type.qualificationlevelDoctoralen_US
dc.type.qualificationnamePhD Doctor of Philosophyen_US
dc.publisher.institutionThe University of St Andrewsen_US
dc.rights.embargodateElectronic copy restricted until 30th November 2017, pending formal approvalen_US
dc.rights.embargoreasonThesis restricted in accordance with University regulationsen_US


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