Abstract
Stereodefined tetrasubstituted alkenes and cycloalkenes, are important moieties, finding applications in pharmaceuticals, materials science, and synthesis. However, their synthesis with control over regio and stereochemistry remains challenging.This thesis describes a novel method for the construction of both stereodefined tetrasubstituted acyclic alkenes and cycloalkenes. The reaction occurs through initial formation of an alkynyl boronate complex via the nucleophilic addition of an alkynyl lithium to a borane followed by Ir-catalyzed enantioselective 1,2-migration/allylation. Finally, mild oxidation gives the more stable tetrasubstituted alkenyl borinic ester.In addition, the syn addition pathway in the intermolecular 1,2-migration/allylation led to further exploration on the intramolecular reaction mode. Through rational design of the starting materials, the in situ generated -allyliridium species-induced 1,2-migration permits similar 1,2-migration/allylation to construct cyclic tetrasubstituted alkenes. This methodology successfully provide a straightforward entry to a diverse range of otherwise inaccessible, enantiomerically enriched, cyclic tetrasubstituted alkenes.
| Date of Award | 10 Dec 2024 |
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| Original language | English |
| Awarding Institution |
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| Supervisor | Adam Noble (Supervisor) & Varinder K Aggarwal (Supervisor) |