Show simple item record

Files in this item

Thumbnail

Item metadata

dc.contributor.advisorClarke, Matt
dc.contributor.authorMartin, Nicola
dc.coverage.spatial89en_US
dc.date.accessioned2011-06-23T15:57:42Z
dc.date.available2011-06-23T15:57:42Z
dc.date.issued2011-06-22
dc.identifier.urihttps://hdl.handle.net/10023/1904
dc.description.abstractThis project involves a study into the hydroformylation of substituted alkenes and ways to exploit “benzylic regioselectivity”. It was our aim to develop a clean, selective hydroformylation reaction which takes advantage of the tendency for benzylic regioselectivity in styrene-type molecules; in doing so, providing a potential route to important biologically active molecules. In Chapter Two, hydroformylation of methyl cinnamate is explored since we envisaged that a regioselective hydroformylation of this substrate would serve as a step in an efficient route to γ-amino acids derivatives; which are important building blocks for the synthesis of important drug molecules. Most Rh-phosphine catalysts install the formyl group α- to the ester group however, we found that certain reaction conditions and appropriate choice of phosphorus containing ligands led to highly chemoselective and regioselective hydroformylation. Regioselectivities of up to 25 : 1 favouring the benzylic aldehyde were observed. However, as will be explained, this reaction is hindered by significant hydrogenation under hydroformylation conditions. Using a novel ligand this side reaction was lowered to 5% with reasonable regioselectivity, however overall conversion to the desired aldehyde was low. As a means to synthesise γ-amino acid derivatives, enamine formation using the aldehyde products was also attempted. An alternative alkenyl arene substrate is studied in Chapter Three. High benzylic regioselectivity was observed using a variety of chiral and achiral ligands and again reaction conditions were optimised with the aim to develop an efficient process for the synthesis of γ-amino alcohol derivatives. It was found that PPh₃, tris(3,4,5-trifluorophenyl)phosphine and a phosphaadamantane cage phosphine ligand gave the most promising results with moderate to high regioselectivity observed. Asymmetric hydroformylation was not possible due to low activity using a variety of state-of-the-art chiral ligands.en_US
dc.language.isoenen_US
dc.publisherUniversity of St Andrews
dc.subjectHydroformylationen_US
dc.subjectOrganometallicen_US
dc.subjectCatalysisen_US
dc.subjectEstersen_US
dc.subject.lccQD281.H79M28
dc.subject.lcshHydroformylationen_US
dc.subject.lcshOrganometallic compoundsen_US
dc.subject.lcshRhodium catalystsen_US
dc.subject.lcshEstersen_US
dc.titleExploring and exploiting benzylic regioselectivity in rhodium-catalysed hydroformylationen_US
dc.typeThesisen_US
dc.type.qualificationlevelDoctoralen_US
dc.type.qualificationnameMPhil Master of Philosophyen_US
dc.publisher.institutionThe University of St Andrewsen_US


This item appears in the following Collection(s)

Show simple item record