Caged Compounds: A Novel Synthesis of Homocubane and its Analogues and Gold-(I) Catalysed Propargylation of Azinium Salts
Publication Date
July 30, 2025
Creator
Abstract
We disclose a novel synthetic method to access the homocubane ester 4a in 4 steps, in an overall yield comparable or superior to literature methods. The sequential transformations of a [6+2] cycloaddition, 4π electrocyclisation, followed by a dehydrogenation and [2+2] cycloaddition displays the relatively simple route to access this challenging to make structure. We also inadvertently synthesised an interesting polycyclic structure we have tentatively assigned as formal [4+2] product 6.
Herein, we report the development of a methodology for the regioselective 1,4-addition of propargyl boronates to a range of N-alkylated pyridinium, quinolinium, and pyrazinium salts, through gold-(I) mediated catalysis. A variety of functionality is tolerated under the mild reaction conditions, and an attempt to rationalise the mechanism has been realised with the assistance of DFT studies. Further potential chemical transformations have also been conducted, which, when combined with the work conducted in this study, pave the way for exploration into underdeveloped and diverse chemical space.
Item Type
ethesis
Thesis Type
PhD
Supervisors
Subjects (LC)
Associated Schools / Departments
School of Chemistry
eprints ID
81034
UoN Repository URI
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Jack Smithson Thesis - Corrected.pdf
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Examined. Jack Smithson Thesis - Corrected
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