Modeling the isomerization of lactones and the role of catalysts in Hetero-Diels-Alder reactions
| dc.contributor | Graduate Program in Chemistry. | |
| dc.contributor.advisor | Aviyente, Viktorya. | |
| dc.contributor.author | Dereli, Büşra. | |
| dc.date.accessioned | 2023-03-16T11:00:22Z | |
| dc.date.available | 2023-03-16T11:00:22Z | |
| dc.date.issued | 2013. | |
| dc.description.abstract | In this study, the isomerization of a strigolactone analogue and the catalyst effect on the hetero-Diels-Alder reactions is investigated by the quantum mechanical tools. In the first part, the interconversion of the strigolactone analogue between its E and Z isomers as well as the atropisomers in an effort to interpret the nature of the isomeric mixture is studied. Density functional theory calculations reveal that a mixture of E and Z isomers can exist concurrently as a result of being formed in the same environment. To the extent of barrier heights which can be surmounted at room temperature, E atropisomers render an affordable interconversion with lower activation energies. On the other hand, Z atropisomers display higher barriers which can be possibly overcome in time. In the second part, transition metal catalyst effect on 1,2-diazine and siloxy alkyne cycloaddition reactions is investigated. Silver(I) as a transition metal plays a crucial role in lowering the activation barriers of 1,2-diazine and siloxy alkyne cycloadditions, which otherwise require thermal conditions. Substitution effect on 1,2-diazine and siloxy alkyne is also taken into account. Relativistic density functional theory calculations prove that the primary role of a metal catalyst in an inverse electron demand Hetero-Diels-Alder reaction is to facilitate the overlap between HOMO of the dienophile and LUMO of the diene by reducing the energy gap. Elucidating the role of catalysis in the 1,2-diazine and siloxy alkyne cycloadditions under mild conditions, possible reaction mechanisms are proposed to shed light on the behavior of the hetero-Diels-Alder reaction. | |
| dc.format.extent | 30 cm. | |
| dc.format.pages | xv, 74 leaves ; | |
| dc.identifier.other | CHEM 2013 D47 | |
| dc.identifier.uri | https://digitalarchive.library.bogazici.edu.tr/handle/123456789/14290 | |
| dc.publisher | Thesis (M.S.) - Bogazici University. Institute for Graduate Studies in Science and Engineering, 2013. | |
| dc.subject.lcsh | Diels-Alder reaction. | |
| dc.subject.lcsh | Heterocyclic compounds. | |
| dc.title | Modeling the isomerization of lactones and the role of catalysts in Hetero-Diels-Alder reactions |
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