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Title: Stereoselective transformations of intramolecular cycloaddition products
Author: Fulgheri, Tamara
ISNI:       0000 0004 7963 6094
Awarding Body: University of Huddersfield
Current Institution: University of Huddersfield
Date of Award: 2019
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In this work, the intramolecular cycloaddition of furan dienes was investigated. At equilibrium, amide-tethered substrates form acyclic precursor : cycloadduct mixtures. Higher portion of cycloadduct proved to be favoured by bulky nitrogen-groups, polar solvents, higher temperature and the presence of some Lewis acids. It was demonstrated that the equilibrium can be displaced by coupling a reversible Diels-Alder cycloaddition to an irreversible and chemoselective reaction, such as Pd-catalysed hydrogenation or mCPBA epoxidation, resulting in the complete transformation of the mixture starting material to the functionalised cycloadduct. A range of asymmetric transformations were also investigated to resolve the racemic mixture derived from the Diels-Alder reaction. The Sharpless dihydroxylation showed a high level of chemoselectivity but it was not able to discriminate between the cycloadduct enantiomers. The Jacobsen epoxidation was not chemoselective but, in absence of Diels-Alder starting material, produced cycloadduct epoxides in modest enantioselectivity via kinetic resolution and dynamic kinetic resolution. Non-symmetrical transformation of the olefin, by asymmetric hydroboration-oxidation, provided regioisomeric alcohols in good enantiomeric excess by regiodivergent resolution.
Supervisor: Gill, Duncan Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Q Science (General) ; QR Microbiology