The versatile chemistry of azidoalkyl enol ethers and their equivalents
<p>This thesis describes the synthesis and intramolecular cycloaddition products of azides tethered to olefins bearing a heteroatom in an attempt to access a proposed triazolium intermediate 77.</p> <p>Chapter 1 covers the synthesis and reactivity of simple di- and trisubstituted a...
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| Format: | Thesis |
| Language: | English |
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2015
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| _version_ | 1826310223436972032 |
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| author | Liddon, JTR |
| author2 | Robertson, J |
| author_facet | Robertson, J Liddon, JTR |
| author_sort | Liddon, JTR |
| collection | OXFORD |
| description | <p>This thesis describes the synthesis and intramolecular cycloaddition products of azides tethered to olefins bearing a heteroatom in an attempt to access a proposed triazolium intermediate 77.</p> <p>Chapter 1 covers the synthesis and reactivity of simple di- and trisubstituted azidoalkyl enol ethers. These substrates were found to provide isolable 1,2,3-triazoline products, but displayed a propensity to aromatise to 1,2,3-triazoles upon ionisation. Difficulties in synthesising fully-substituted azidoalkyl enol ethers have precluded a detailed study in this project, though a bias towards α-alkoxy imine formation was suggested.</p> <p>Chapter 2 covers the chemistry of azidoalkyl vinyl bromides. Simple vinyl bromide substrates were found to yield 1-azadienes upon thermolysis, presumably <em>via</em> the dehydrobromination of an α-bromo imine intermediate <em>in situ</em>.</p> <p>In Chapter 3, a brief diversity-oriented synthesis (DOS) campaign was undertaken to demonstrate the potent reactivity of 1-azadiene substrates. 1-Azadienes were found to be versatile intermediates, and a small DOS library was built by exploiting several key reactivity modes.</p> <p>In Chapter 4, two miscellaneous routes towards the desired triazolium intermediate are discussed, and finally an Appendix chapter deals with an attempted total synthesis of salinosporamide C.</p> |
| first_indexed | 2024-03-07T07:47:18Z |
| format | Thesis |
| id | oxford-uuid:a5554d44-d251-4ca5-8b2d-d07a7c95138a |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T07:47:18Z |
| publishDate | 2015 |
| record_format | dspace |
| spelling | oxford-uuid:a5554d44-d251-4ca5-8b2d-d07a7c95138a2023-06-16T08:24:07ZThe versatile chemistry of azidoalkyl enol ethers and their equivalentsThesishttp://purl.org/coar/resource_type/c_db06uuid:a5554d44-d251-4ca5-8b2d-d07a7c95138aOrganicChemistryOrganic ChemistryEnglishOxford University Research Archive - Valet2015Liddon, JTRRobertson, J<p>This thesis describes the synthesis and intramolecular cycloaddition products of azides tethered to olefins bearing a heteroatom in an attempt to access a proposed triazolium intermediate 77.</p> <p>Chapter 1 covers the synthesis and reactivity of simple di- and trisubstituted azidoalkyl enol ethers. These substrates were found to provide isolable 1,2,3-triazoline products, but displayed a propensity to aromatise to 1,2,3-triazoles upon ionisation. Difficulties in synthesising fully-substituted azidoalkyl enol ethers have precluded a detailed study in this project, though a bias towards α-alkoxy imine formation was suggested.</p> <p>Chapter 2 covers the chemistry of azidoalkyl vinyl bromides. Simple vinyl bromide substrates were found to yield 1-azadienes upon thermolysis, presumably <em>via</em> the dehydrobromination of an α-bromo imine intermediate <em>in situ</em>.</p> <p>In Chapter 3, a brief diversity-oriented synthesis (DOS) campaign was undertaken to demonstrate the potent reactivity of 1-azadiene substrates. 1-Azadienes were found to be versatile intermediates, and a small DOS library was built by exploiting several key reactivity modes.</p> <p>In Chapter 4, two miscellaneous routes towards the desired triazolium intermediate are discussed, and finally an Appendix chapter deals with an attempted total synthesis of salinosporamide C.</p> |
| spellingShingle | Organic Chemistry Organic Chemistry Liddon, JTR The versatile chemistry of azidoalkyl enol ethers and their equivalents |
| title | The versatile chemistry of azidoalkyl enol ethers and their equivalents |
| title_full | The versatile chemistry of azidoalkyl enol ethers and their equivalents |
| title_fullStr | The versatile chemistry of azidoalkyl enol ethers and their equivalents |
| title_full_unstemmed | The versatile chemistry of azidoalkyl enol ethers and their equivalents |
| title_short | The versatile chemistry of azidoalkyl enol ethers and their equivalents |
| title_sort | versatile chemistry of azidoalkyl enol ethers and their equivalents |
| topic | Organic Chemistry Organic Chemistry |
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