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dc.contributor.advisorDervan, Peter B.
dc.contributor.authorEichelsheim, Tanja
dc.coverage.spatialvi, 111en_US
dc.date.accessioned2012-10-05T08:31:56Z
dc.date.available2012-10-05T08:31:56Z
dc.date.issued2012-11-30
dc.identifieruk.bl.ethos.558122
dc.identifier.urihttps://hdl.handle.net/10023/3168
dc.description.abstractCatalysis plays an important part in our society. Numerous transition metal catalysts have been developed which can convert many different substrates in a wide range of reactions. Catalysis also plays an important role in nature and therefore special catalysts, enzymes, have evolved over time. Enzymes are tremendously efficient giving high yields and selectivities both regio and chemical but have a limited substrate and reaction scope. It was speculated that by combining the two, an ideal catalyst can be obtained. We planned to achieve this by introducing a transition metal, the catalytic centre, into the chiral environment of a double helical oligonucleotide. The transition metals were introduced by coordinating them to a ligand which was located in the chiral environment of a double helix. The ligand was either covalently bound (Chapter 2) or non-covalently bound (Chapter 3) to the oligonucleotide. For the covalent approach a phosphine ligand was chosen. A nucleoside was modified with an alkyne to which a phosphine moiety could be coupled via the copper catalysed 1,3-dipolar cycloaddition. The modified nucleoside was incorporated into an oligonucleotide before attempting to attach the phosphine moiety. The monomer was used as a ligand in allylic substitution and hydroformylation. In the non-covalent approach polyamide minor groove binders were functionalised with an amine linker. Phosphine moieties were connected via amide bond formation. Although the coupling worked effortlessly the phosphines oxidised during purification therefore dienes were also investigated.en_US
dc.language.isoenen_US
dc.publisherUniversity of St Andrews
dc.rightsCreative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/3.0/
dc.subjectDNAen_US
dc.subjectCatalysis in aqueous mediaen_US
dc.subjectAllylic substitutionen_US
dc.subjectHydroformylationen_US
dc.subjectTransition metals: palladium and iridiumen_US
dc.subject.lccQD505.E5
dc.subject.lcshCatalysisen_US
dc.subject.lcshTransition metal catalystsen_US
dc.subject.lcshEnzymesen_US
dc.subject.lcshOligonucleotidesen_US
dc.subject.lcshDNAen_US
dc.titleOligonucleotide based ligands in homogeneous transition metal catalysisen_US
dc.typeThesisen_US
dc.type.qualificationlevelDoctoralen_US
dc.type.qualificationnamePhD Doctor of Philosophyen_US
dc.publisher.institutionThe University of St Andrewsen_US
dc.publisher.departmentCalifornia institute of Technologyen_US


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Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported
Except where otherwise noted within the work, this item's licence for re-use is described as Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported