Diasterodivergent synthesis of fused ring systems
<p><b>Introduction</b></p> <p>We envisioned using phase transfer catalysis (PTC) to develop asymmetric carba-6π- electrocyclisations. We believed that the configurational lability of 6π systems could be reduced by constraining them within a ring system.</p> <...
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| Other Authors: | |
| Format: | Thesis |
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2015
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| _version_ | 1797062769892130816 |
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| author | Kiss, E |
| author2 | Smith, M |
| author_facet | Smith, M Kiss, E |
| author_sort | Kiss, E |
| collection | OXFORD |
| description | <p><b>Introduction</b></p> <p>We envisioned using phase transfer catalysis (PTC) to develop asymmetric carba-6π- electrocyclisations. We believed that the configurational lability of 6π systems could be reduced by constraining them within a ring system.</p> <p><b>Results and Discussion</b></p> <p>En route to the synthesis of a starting material for the transannular electrocyclisation reaction, we noticed that a 5-5-3 fused ring system had formed, in one step, from a linear precursor and as a single diastereomer. We synthesised both geometric isomers of the starting materials, and unexpectedly, the E or Z isomers cyclised to form different products under different reaction conditions. We further investigated the 5-5-3 system, generating substrate scope and computationally and experimentally exploring the mechanism.</p> <p><b>Conclusion</b></p> <p>In one step we have constructed three carbon-carbon bonds, up to five contiguous stereogenic centres and all as a single diastereomer. We have synthesised 15 examples and have probed the mechanism experimentally and computationally. We have also investigated asymmetric examples of this reaction.</p> |
| first_indexed | 2024-03-06T20:50:19Z |
| format | Thesis |
| id | oxford-uuid:37545702-38f9-4bb5-a233-69a296387792 |
| institution | University of Oxford |
| last_indexed | 2024-03-06T20:50:19Z |
| publishDate | 2015 |
| record_format | dspace |
| spelling | oxford-uuid:37545702-38f9-4bb5-a233-69a2963877922022-03-26T13:43:28ZDiasterodivergent synthesis of fused ring systemsThesishttp://purl.org/coar/resource_type/c_db06uuid:37545702-38f9-4bb5-a233-69a296387792ORA Deposit2015Kiss, ESmith, M<p><b>Introduction</b></p> <p>We envisioned using phase transfer catalysis (PTC) to develop asymmetric carba-6π- electrocyclisations. We believed that the configurational lability of 6π systems could be reduced by constraining them within a ring system.</p> <p><b>Results and Discussion</b></p> <p>En route to the synthesis of a starting material for the transannular electrocyclisation reaction, we noticed that a 5-5-3 fused ring system had formed, in one step, from a linear precursor and as a single diastereomer. We synthesised both geometric isomers of the starting materials, and unexpectedly, the E or Z isomers cyclised to form different products under different reaction conditions. We further investigated the 5-5-3 system, generating substrate scope and computationally and experimentally exploring the mechanism.</p> <p><b>Conclusion</b></p> <p>In one step we have constructed three carbon-carbon bonds, up to five contiguous stereogenic centres and all as a single diastereomer. We have synthesised 15 examples and have probed the mechanism experimentally and computationally. We have also investigated asymmetric examples of this reaction.</p> |
| spellingShingle | Kiss, E Diasterodivergent synthesis of fused ring systems |
| title | Diasterodivergent synthesis of fused ring systems |
| title_full | Diasterodivergent synthesis of fused ring systems |
| title_fullStr | Diasterodivergent synthesis of fused ring systems |
| title_full_unstemmed | Diasterodivergent synthesis of fused ring systems |
| title_short | Diasterodivergent synthesis of fused ring systems |
| title_sort | diasterodivergent synthesis of fused ring systems |
| work_keys_str_mv | AT kisse diasterodivergentsynthesisoffusedringsystems |