Development of functional group tolerant and room temperature hydrogen borrowing enolate alkylation reactions
<p>This thesis describes work completed to expand the scope of hydrogen borrowing enolate alkylation reactions. It was hypothesised that the development of a room temperature reaction would allow utility of a breadth of chemical space previously undemonstrated in these reactions at high temper...
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| Format: | Thesis |
| Language: | English |
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2023
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| _version_ | 1797112098134687744 |
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| author | Bailey, EP |
| author2 | Smith, M |
| author_facet | Smith, M Bailey, EP |
| author_sort | Bailey, EP |
| collection | OXFORD |
| description | <p>This thesis describes work completed to expand the scope of hydrogen borrowing enolate alkylation reactions. It was hypothesised that the development of a room temperature reaction would allow utility of a breadth of chemical space previously undemonstrated in these reactions at high temperatures (80–180°C). The first strategy to achieve this was via the generation of excited state intermediates of the hydrogen borrowing cycle using visible light energy and a designed catalyst. A room temperature visible light driven reaction was realised and detailed mechanistic studies unveiled the role of visible light.</p>
<p>Later a light independent room temperature reaction was discovered and further developed to vastly expand the usable chemical space in hydrogen borrowing enolate alkylation reactions. A diverse range of nitrogen rich heterocycles were also demonstrated at higher temperatures (85°C) and mechanistic studies explained the need for anaerobic conditions in the reaction at room temperature.</p> |
| first_indexed | 2024-03-07T08:19:09Z |
| format | Thesis |
| id | oxford-uuid:ba2a8b5f-258b-4446-be3b-d809c6f1fd2d |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T08:19:09Z |
| publishDate | 2023 |
| record_format | dspace |
| spelling | oxford-uuid:ba2a8b5f-258b-4446-be3b-d809c6f1fd2d2024-01-22T09:01:57ZDevelopment of functional group tolerant and room temperature hydrogen borrowing enolate alkylation reactionsThesishttp://purl.org/coar/resource_type/c_db06uuid:ba2a8b5f-258b-4446-be3b-d809c6f1fd2dEnolate AlkylationHydrogen BorrowingBorrowing HydrogenIridiumCatalysisKetone AlkylationChemistry, OrganicAlcoholsOrganometallic chemistryOrganic ChemistryMethodologyMechanismIridium hydridesHomogeneous catalysisPhotochemistryKetonesMechanistic StudiesEnglishHyrax Deposit2023Bailey, EPSmith, MDonohoe, TWillis, MBower, J<p>This thesis describes work completed to expand the scope of hydrogen borrowing enolate alkylation reactions. It was hypothesised that the development of a room temperature reaction would allow utility of a breadth of chemical space previously undemonstrated in these reactions at high temperatures (80–180°C). The first strategy to achieve this was via the generation of excited state intermediates of the hydrogen borrowing cycle using visible light energy and a designed catalyst. A room temperature visible light driven reaction was realised and detailed mechanistic studies unveiled the role of visible light.</p> <p>Later a light independent room temperature reaction was discovered and further developed to vastly expand the usable chemical space in hydrogen borrowing enolate alkylation reactions. A diverse range of nitrogen rich heterocycles were also demonstrated at higher temperatures (85°C) and mechanistic studies explained the need for anaerobic conditions in the reaction at room temperature.</p> |
| spellingShingle | Enolate Alkylation Hydrogen Borrowing Borrowing Hydrogen Iridium Catalysis Ketone Alkylation Chemistry, Organic Alcohols Organometallic chemistry Organic Chemistry Methodology Mechanism Iridium hydrides Homogeneous catalysis Photochemistry Ketones Mechanistic Studies Bailey, EP Development of functional group tolerant and room temperature hydrogen borrowing enolate alkylation reactions |
| title | Development of functional group tolerant and room temperature hydrogen borrowing enolate alkylation reactions |
| title_full | Development of functional group tolerant and room temperature hydrogen borrowing enolate alkylation reactions |
| title_fullStr | Development of functional group tolerant and room temperature hydrogen borrowing enolate alkylation reactions |
| title_full_unstemmed | Development of functional group tolerant and room temperature hydrogen borrowing enolate alkylation reactions |
| title_short | Development of functional group tolerant and room temperature hydrogen borrowing enolate alkylation reactions |
| title_sort | development of functional group tolerant and room temperature hydrogen borrowing enolate alkylation reactions |
| topic | Enolate Alkylation Hydrogen Borrowing Borrowing Hydrogen Iridium Catalysis Ketone Alkylation Chemistry, Organic Alcohols Organometallic chemistry Organic Chemistry Methodology Mechanism Iridium hydrides Homogeneous catalysis Photochemistry Ketones Mechanistic Studies |
| work_keys_str_mv | AT baileyep developmentoffunctionalgrouptolerantandroomtemperaturehydrogenborrowingenolatealkylationreactions |