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dc.contributor.advisorSchneider, Uwe
dc.contributor.advisorLam, Hon
dc.contributor.authorHepburn, Hamish Bruce
dc.date.accessioned2016-11-08T12:26:06Z
dc.date.available2016-11-08T12:26:06Z
dc.date.issued2015-06-30
dc.identifier.urihttp://hdl.handle.net/1842/17614
dc.description.abstractA highly enantioselective and diastereoselective rhodium-catalysed addition of potassium allyltrifluoroborates to cyclic imines is described within. By utilising rhodium-chiral diene complexes, a wide range of cyclic imines were successfully allylated in high yields and enantioselectivities. Using a variety of more highly substituted allyl reagents, additional stereocentres and further molecular complexity was achieved with good yields, enantioselectivities and diastereoselectivities. Investigations involving isomeric allyl species and deuterated allyl species provided results that gave mechanistic insight, leading to the proposal of a plausible mechanistic pathway and suggested the formation of interconverting allylrhodium intermediates. Furthermore, during these investigations, a highly interesting isomerisation of the allylrhodium intermediate was discovered. Such isomerisation led to the in situ formation of the more complex allylrhodium intermediates which led to complex products upon allylation with cyclic imines that would be difficult to synthesis via other methods. This isomerisation was found to occur for a range of cyclic imines and disubstituted allyltrifluoroborates, proceeding in good yields and diastereomeric ratios. Deuterium studies indicate it is probable that this isomerisation proceeds via a 1,4 rhodium migration and a plausible mechanism is proposed explaining both the connectivity of the products and the relative stereochemistry.en
dc.contributor.sponsorEngineering and Physical Sciences Research Council (EPSRC)en
dc.language.isoenen
dc.publisherThe University of Edinburghen
dc.relation.hasversionLuo, Y.; Hepburn, H. B.; Chotsaeng, N.; Lam, H. W. Angew. Chem., Int. Ed. 2012, 51, 8309-8313.en
dc.relation.hasversionHepburn H. B.; Chotsaeng, N.; Luo, Y.; Lam, H. W. Synthesis, 2013, 45, 2649-2661.en
dc.relation.hasversionHepburn, H. B.; Lam, H. W. Angew. Chem. Int. Ed. 2014, 53, 11605-11610.en
dc.subjectrhodiumen
dc.subjectenantioselectiveen
dc.subjectdieneen
dc.titleEnantioselective rhodium-catalysed nucleophilic allylation of cyclic iminesen
dc.typeThesis or Dissertationen
dc.type.qualificationlevelDoctoralen
dc.type.qualificationnamePhD Doctor of Philosophyen
dc.rights.embargodate2100-12-31en
dcterms.accessRightsRestricted Accessen


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