Malonyl radical cyclisations in heteroaromatic functionalisation and natural product synthesis
<p>This thesis describes the application of malonyl radical cyclisations to the synthesis of annulated heteroaromatics and towards the formal synthesis of ginkgolide B (<strong>V</strong>). It is divided into three chapters:</p> <p><strong>Chapter 1</strong>...
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| Format: | Thesis |
| Language: | English |
| Published: |
2023
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| _version_ | 1826315803474001920 |
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| author | Hernández Lladó, P |
| author2 | Burton, J |
| author_facet | Burton, J Hernández Lladó, P |
| author_sort | Hernández Lladó, P |
| collection | OXFORD |
| description | <p>This thesis describes the application of malonyl radical cyclisations to the synthesis of annulated heteroaromatics and towards the formal synthesis of ginkgolide B (<strong>V</strong>). It is divided into three chapters:</p>
<p><strong>Chapter 1</strong> provides a general introduction to the generation and reactivity of malonyl radicals as well as a summary of their applications in organic synthesis.</p>
<p><strong>Chapter 2</strong> reviews the available methods for the synthesis of annulated heteroaromatics (<strong>III</strong>) and describes the development and application of a new, malonyl radical-based, photochemical method for their synthesis. This method is based on the photolysis of in situ generated iodomalonates (<strong>I</strong>) and builds on previous work in the Burton group. Our investigations into the mechanism of this transformation are also detailed in this chapter.</p>
<p><strong>Chapter 3</strong> covers our efforts towards the formal synthesis of ginkgolide B (<strong>V</strong>) via a malonyl radical cascade. It details the investigation of two different routes and the elaboration of a product of the radical cascade into the core of the natural product (<strong>IV</strong>). This chapter also describes the enantioselective synthesis of a key intermediate via an organocatalysed Michael addition. Finally, it suggests a synthetic plan to complete the asymmetric formal synthesis of ginkgolide B (<strong>V</strong>).</p> |
| first_indexed | 2024-03-07T07:49:30Z |
| format | Thesis |
| id | oxford-uuid:1af671c2-7108-4cb0-be29-4c61702ae1be |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-12-09T03:32:54Z |
| publishDate | 2023 |
| record_format | dspace |
| spelling | oxford-uuid:1af671c2-7108-4cb0-be29-4c61702ae1be2024-12-01T16:02:07ZMalonyl radical cyclisations in heteroaromatic functionalisation and natural product synthesisThesishttp://purl.org/coar/resource_type/c_db06uuid:1af671c2-7108-4cb0-be29-4c61702ae1beChemistry, OrganicEnglishHyrax Deposit2023Hernández Lladó, PBurton, J<p>This thesis describes the application of malonyl radical cyclisations to the synthesis of annulated heteroaromatics and towards the formal synthesis of ginkgolide B (<strong>V</strong>). It is divided into three chapters:</p> <p><strong>Chapter 1</strong> provides a general introduction to the generation and reactivity of malonyl radicals as well as a summary of their applications in organic synthesis.</p> <p><strong>Chapter 2</strong> reviews the available methods for the synthesis of annulated heteroaromatics (<strong>III</strong>) and describes the development and application of a new, malonyl radical-based, photochemical method for their synthesis. This method is based on the photolysis of in situ generated iodomalonates (<strong>I</strong>) and builds on previous work in the Burton group. Our investigations into the mechanism of this transformation are also detailed in this chapter.</p> <p><strong>Chapter 3</strong> covers our efforts towards the formal synthesis of ginkgolide B (<strong>V</strong>) via a malonyl radical cascade. It details the investigation of two different routes and the elaboration of a product of the radical cascade into the core of the natural product (<strong>IV</strong>). This chapter also describes the enantioselective synthesis of a key intermediate via an organocatalysed Michael addition. Finally, it suggests a synthetic plan to complete the asymmetric formal synthesis of ginkgolide B (<strong>V</strong>).</p> |
| spellingShingle | Chemistry, Organic Hernández Lladó, P Malonyl radical cyclisations in heteroaromatic functionalisation and natural product synthesis |
| title | Malonyl radical cyclisations in heteroaromatic functionalisation and natural product synthesis |
| title_full | Malonyl radical cyclisations in heteroaromatic functionalisation and natural product synthesis |
| title_fullStr | Malonyl radical cyclisations in heteroaromatic functionalisation and natural product synthesis |
| title_full_unstemmed | Malonyl radical cyclisations in heteroaromatic functionalisation and natural product synthesis |
| title_short | Malonyl radical cyclisations in heteroaromatic functionalisation and natural product synthesis |
| title_sort | malonyl radical cyclisations in heteroaromatic functionalisation and natural product synthesis |
| topic | Chemistry, Organic |
| work_keys_str_mv | AT hernandezlladop malonylradicalcyclisationsinheteroaromaticfunctionalisationandnaturalproductsynthesis |