Development of cation-directed acylation reactions
<p>This thesis describes work conducted towards the enantioselective acylation of ketones using phase-transfer catalysis. Chapter 1 introduces the field of ketone acylation, with a focus on catalytic methods accompanied by the generation of axes, planes or points of chirality during these t...
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| その他の著者: | |
| フォーマット: | 学位論文 |
| 出版事項: |
2018
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| _version_ | 1826315516720971776 |
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| author | Rahemtulla, B |
| author2 | Smith, M |
| author_facet | Smith, M Rahemtulla, B |
| author_sort | Rahemtulla, B |
| collection | OXFORD |
| description | <p>This thesis describes work conducted towards the enantioselective acylation of ketones using phase-transfer catalysis. Chapter 1 introduces the field of ketone acylation, with a focus on catalytic methods accompanied by the generation of axes, planes or points of chirality during these transformations. Chapters 2 describes the synthesis and evaluation of a variety of different frameworks for enantioselective ketone O-acylation; we highlight the selectivity and reactivity challenges faced when attempting this transformation (Scheme I).</p> <p>Chapter 3 focuses on the intramolecular O-acylation of enolates to generate axially chiral lactones. The development of these systems led to the discovery that the C/O-selectivity of this reaction was dependent on the steric hindrance about the axis of rotation, and C-acylation could be favoured under the correct conditions.</p> <p>Chapter 4 describes the conception and development of an enantioselective C-acylation reaction, culminating in the first reported catalytic enantioselective direct C-acylation of a ketone (Scheme II). The scope and limitations of this methodology were investigated and the products were successfully elaborated to afford a range of spirocyclic architectures.</p> <p>Finally, chapter 5 focuses on the kinetic analysis of the enantioselective C-acylation reaction in order to increase our understanding of the mechanisms behind phase-transfer catalysis and the mode of activation of the catalyst.</p> |
| first_indexed | 2024-03-06T18:22:25Z |
| format | Thesis |
| id | oxford-uuid:06bfa464-4c5c-47d7-a35c-9cf60576dec4 |
| institution | University of Oxford |
| last_indexed | 2024-12-09T03:27:29Z |
| publishDate | 2018 |
| record_format | dspace |
| spelling | oxford-uuid:06bfa464-4c5c-47d7-a35c-9cf60576dec42024-12-01T10:23:34ZDevelopment of cation-directed acylation reactionsThesishttp://purl.org/coar/resource_type/c_db06uuid:06bfa464-4c5c-47d7-a35c-9cf60576dec4ORA Deposit2018Rahemtulla, BSmith, MClark, H<p>This thesis describes work conducted towards the enantioselective acylation of ketones using phase-transfer catalysis. Chapter 1 introduces the field of ketone acylation, with a focus on catalytic methods accompanied by the generation of axes, planes or points of chirality during these transformations. Chapters 2 describes the synthesis and evaluation of a variety of different frameworks for enantioselective ketone O-acylation; we highlight the selectivity and reactivity challenges faced when attempting this transformation (Scheme I).</p> <p>Chapter 3 focuses on the intramolecular O-acylation of enolates to generate axially chiral lactones. The development of these systems led to the discovery that the C/O-selectivity of this reaction was dependent on the steric hindrance about the axis of rotation, and C-acylation could be favoured under the correct conditions.</p> <p>Chapter 4 describes the conception and development of an enantioselective C-acylation reaction, culminating in the first reported catalytic enantioselective direct C-acylation of a ketone (Scheme II). The scope and limitations of this methodology were investigated and the products were successfully elaborated to afford a range of spirocyclic architectures.</p> <p>Finally, chapter 5 focuses on the kinetic analysis of the enantioselective C-acylation reaction in order to increase our understanding of the mechanisms behind phase-transfer catalysis and the mode of activation of the catalyst.</p> |
| spellingShingle | Rahemtulla, B Development of cation-directed acylation reactions |
| title | Development of cation-directed acylation reactions |
| title_full | Development of cation-directed acylation reactions |
| title_fullStr | Development of cation-directed acylation reactions |
| title_full_unstemmed | Development of cation-directed acylation reactions |
| title_short | Development of cation-directed acylation reactions |
| title_sort | development of cation directed acylation reactions |
| work_keys_str_mv | AT rahemtullab developmentofcationdirectedacylationreactions |