Caged Compounds: A Novel Synthesis of Homocubane and its Analogues and Gold-(I) Catalysed Propargylation of Azinium Salts
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 rela...
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| Format: | Thesis (University of Nottingham only) |
| Language: | English |
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2025
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| Online Access: | https://eprints.nottingham.ac.uk/81034/ |
| _version_ | 1848801289594470400 |
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| author | Smithson, Jack |
| author_facet | Smithson, Jack |
| author_sort | Smithson, Jack |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T21:05:05Z |
| format | Thesis (University of Nottingham only) |
| id | nottingham-81034 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T21:05:05Z |
| publishDate | 2025 |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-810342025-07-30T04:40:18Z https://eprints.nottingham.ac.uk/81034/ Caged Compounds: A Novel Synthesis of Homocubane and its Analogues and Gold-(I) Catalysed Propargylation of Azinium Salts Smithson, Jack 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. 2025-07-30 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en cc_by https://eprints.nottingham.ac.uk/81034/1/Jack%20Smithson%20Thesis%20-%20Corrected.pdf 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. propargylation caged compounds catalysis DFT studies gold mechanism |
| spellingShingle | propargylation caged compounds catalysis DFT studies gold mechanism Smithson, Jack Caged Compounds: A Novel Synthesis of Homocubane and its Analogues and Gold-(I) Catalysed Propargylation of Azinium Salts |
| title | Caged Compounds: A Novel Synthesis of Homocubane and its Analogues and Gold-(I) Catalysed Propargylation of Azinium Salts |
| title_full | Caged Compounds: A Novel Synthesis of Homocubane and its Analogues and Gold-(I) Catalysed Propargylation of Azinium Salts |
| title_fullStr | Caged Compounds: A Novel Synthesis of Homocubane and its Analogues and Gold-(I) Catalysed Propargylation of Azinium Salts |
| title_full_unstemmed | Caged Compounds: A Novel Synthesis of Homocubane and its Analogues and Gold-(I) Catalysed Propargylation of Azinium Salts |
| title_short | Caged Compounds: A Novel Synthesis of Homocubane and its Analogues and Gold-(I) Catalysed Propargylation of Azinium Salts |
| title_sort | caged compounds: a novel synthesis of homocubane and its analogues and gold-(i) catalysed propargylation of azinium salts |
| topic | propargylation caged compounds catalysis DFT studies gold mechanism |
| url | https://eprints.nottingham.ac.uk/81034/ |