dc.contributor.advisor | Connon, Stephen | |
dc.contributor.author | Cornaggia, Claudio | |
dc.date.accessioned | 2019-11-05T15:11:49Z | |
dc.date.available | 2019-11-05T15:11:49Z | |
dc.date.issued | 2013 | |
dc.identifier.citation | Claudio Cornaggia, 'Novel biomimetic organocatalysts and asymmetric formal cycloaddition reactions using enolisable anhydrides as nucleophiles', [thesis], Trinity College (Dublin, Ireland). School of Chemistry, 2013, pp 338 | |
dc.identifier.other | THESIS 10108 | |
dc.identifier.uri | http://hdl.handle.net/2262/90057 | |
dc.description.abstract | The synthesis of a biomimetic organocatalyst bearing functional groups mimicking the
active residues in the active site of the oxidoreductase enzyme non-phosphorylating
glyceraldehyde-3-phosphate dehydrogenase (GAPN) has been undertaken. Analogues
of GAPN having a Cys-mimicking thiol group, a Asn- mimicking amide functionality
but devoid of a NAD+ -mimicking pyridinium ion were prepared and evaluated in the
reaction with aldehydes to form hemithioacetal species, which is the first step of the
overall oxidation reaction catalysed by the natural enzyme GAPN. For the first time the
reactivity of a Cys-mimicking thiol group was exploited in a biomimetic oxidation and
we could observe that in our enzyme mimics, acid catalysis (in the form of hydrogenbond
donation) was not involved in the hemithioacetal-forming step. Attempts to
imitate the hydride transfer step of the biochemical pathway failed repeatedly due to the
instability of the enzyme mimic under the reaction conditions. | |
dc.format | 1 volume | |
dc.language.iso | en | |
dc.publisher | Trinity College (Dublin, Ireland). School of Chemistry | |
dc.relation.isversionof | http://stella.catalogue.tcd.ie/iii/encore/record/C__Rb15355272 | |
dc.subject | Chemistry, Ph.D. | |
dc.subject | Ph.D. Trinity College Dublin. | |
dc.title | Novel biomimetic organocatalysts and asymmetric formal cycloaddition reactions using enolisable anhydrides as nucleophiles | |
dc.type | thesis | |
dc.type.supercollection | thesis_dissertations | |
dc.type.supercollection | refereed_publications | |
dc.type.qualificationlevel | Doctoral | |
dc.type.qualificationname | Doctor of Philosophy (Ph.D.) | |
dc.rights.ecaccessrights | openAccess | |
dc.format.extentpagination | pp 338 | |
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