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Smithson, Jack (2025) Caged Compounds: A Novel Synthesis of Homocubane and its Analogues and Gold-(I) Catalysed Propargylation of Azinium Salts. PhD thesis, University of Nottingham.

PDF (Jack Smithson Thesis - Corrected) (Thesis - as examined) - Repository staff only until 30 July 2027. Subsequently available to Anyone - Requires a PDF viewer such as GSview, Xpdf or Adobe Acrobat Reader Available under Licence Creative Commons Attribution. Download (8MB)

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:	Thesis (University of Nottingham only) (PhD)
Supervisors:	Lam, Hon Wai Woodward, Simon
Keywords:	propargylation, caged compounds, catalysis, DFT studies, gold, mechanism
Subjects:	Q Science > QD Chemistry > QD241 Organic chemistry
Faculties/Schools:	UK Campuses > Faculty of Science > School of Chemistry
Item ID:	81034
Depositing User:	Smithson, Jack
Date Deposited:	30 Jul 2025 04:40
Last Modified:	30 Jul 2025 04:40
URI:	https://eprints.nottingham.ac.uk/id/eprint/81034

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