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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| Summary: | <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> |
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