Development and applications of rhodium-catalysed reactions to explore the synthesis of heterocycles
<p>This thesis, submitted for the degree of Doctor of Philosophy in Organic Chemistry, documents new methodologies towards the synthesis of saturated heterocycles. These methods utilise a variety of novel <em>S</em>- and <em>N</em>-chelating alkenyl aldehyde substrate...
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| Other Authors: | |
| Format: | Thesis |
| Language: | English |
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2016
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| _version_ | 1817932135668908032 |
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| author | Niu, J |
| author2 | Willis, M |
| author_facet | Willis, M Niu, J |
| author_sort | Niu, J |
| collection | OXFORD |
| description | <p>This thesis, submitted for the degree of Doctor of Philosophy in Organic Chemistry, documents new methodologies towards the synthesis of saturated heterocycles. These methods utilise a variety of novel <em>S</em>- and <em>N</em>-chelating alkenyl aldehyde substrates, and exploit a Rh(I)-catalytic system for the coupling of these aldehydes with alkynes, alkenes and boronic acids.</p> <p>Chapter 1 presents a literature review surveying the development of both intramolecular and intermolecular rhodium-catalysed hydroacylation, paying particular attention to the use of chelating substrates to promote hydroacylation and suppress the decarbonylation process. The importance of <em>N</em>-heterocycles in pharmaceutical and natural products is also documented.</p> <p>Chapter 2 demonstrates the use of heterocycle-derived <em>β</em>-S-enals as bifunctional substrates in a rhodium-catalysed hydroacylation / Suzuki coupling sequence, resulting in the threecomponent assembly of heterocyclic product. An intensive study of the derivatization of the substituted heterocyclic products is also described.</p> <br/><p align="center"><img alt="Figure.1" src="https://ora.ox.ac.uk/objects/uuid:1bea588d-c54e-429a-8e12-66de38ffb3ad/datastreams/content02" style="width:364px;height:132px;"/></p><br/> <p>Chapter 3 presents a kinetic resolution study on tropane derivatives using the rhodiumcatalysed alkyne hydroacylation reaction. A wide range of chiral phosphine ligands and a variation of reaction conditions and chelating groups have been explored.</p> <br/><p align="center"><img alt="Figure.2" src="https://ora.ox.ac.uk/objects/uuid:1bea588d-c54e-429a-8e12-66de38ffb3ad/datastreams/content03" style="width:364px;height:132px;"/></p><br/> <p>Chapter 4 documents an investigation of the rhodium-catalysed hydroacylation reaction using <em>N</em>-chelating alkenyl aldehyde substrates. A variety of <em>β</em>-aminoenal precursors were obtained using the Buchwald-Hartwig amination. The optimisation of the reaction conditions using various <em>bis</em>-phosphine ligands with different chelating groups has been documented. A brief alkyne and alkene component scope is also included.</p> <br/><p align="center"><img alt="Figure.3" src="https://ora.ox.ac.uk/objects/uuid:1bea588d-c54e-429a-8e12-66de38ffb3ad/datastreams/content04" style="width:364px;height:132px;"/></p><br/> <p>Chapter 5 documents the experimental data.</p> <p>Appendix presents <sup>1</sup>H, <sup>13</sup>C and <sup>19</sup>F NMR spectra of novel compounds and chiral HPLC data.</p> |
| first_indexed | 2024-03-06T19:26:33Z |
| format | Thesis |
| id | oxford-uuid:1bea588d-c54e-429a-8e12-66de38ffb3ad |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-12-09T03:33:06Z |
| publishDate | 2016 |
| record_format | dspace |
| spelling | oxford-uuid:1bea588d-c54e-429a-8e12-66de38ffb3ad2024-12-01T16:16:27ZDevelopment and applications of rhodium-catalysed reactions to explore the synthesis of heterocyclesThesishttp://purl.org/coar/resource_type/c_db06uuid:1bea588d-c54e-429a-8e12-66de38ffb3adEnglishORA Deposit2016Niu, JWillis, M<p>This thesis, submitted for the degree of Doctor of Philosophy in Organic Chemistry, documents new methodologies towards the synthesis of saturated heterocycles. These methods utilise a variety of novel <em>S</em>- and <em>N</em>-chelating alkenyl aldehyde substrates, and exploit a Rh(I)-catalytic system for the coupling of these aldehydes with alkynes, alkenes and boronic acids.</p> <p>Chapter 1 presents a literature review surveying the development of both intramolecular and intermolecular rhodium-catalysed hydroacylation, paying particular attention to the use of chelating substrates to promote hydroacylation and suppress the decarbonylation process. The importance of <em>N</em>-heterocycles in pharmaceutical and natural products is also documented.</p> <p>Chapter 2 demonstrates the use of heterocycle-derived <em>β</em>-S-enals as bifunctional substrates in a rhodium-catalysed hydroacylation / Suzuki coupling sequence, resulting in the threecomponent assembly of heterocyclic product. An intensive study of the derivatization of the substituted heterocyclic products is also described.</p> <br/><p align="center"><img alt="Figure.1" src="https://ora.ox.ac.uk/objects/uuid:1bea588d-c54e-429a-8e12-66de38ffb3ad/datastreams/content02" style="width:364px;height:132px;"/></p><br/> <p>Chapter 3 presents a kinetic resolution study on tropane derivatives using the rhodiumcatalysed alkyne hydroacylation reaction. A wide range of chiral phosphine ligands and a variation of reaction conditions and chelating groups have been explored.</p> <br/><p align="center"><img alt="Figure.2" src="https://ora.ox.ac.uk/objects/uuid:1bea588d-c54e-429a-8e12-66de38ffb3ad/datastreams/content03" style="width:364px;height:132px;"/></p><br/> <p>Chapter 4 documents an investigation of the rhodium-catalysed hydroacylation reaction using <em>N</em>-chelating alkenyl aldehyde substrates. A variety of <em>β</em>-aminoenal precursors were obtained using the Buchwald-Hartwig amination. The optimisation of the reaction conditions using various <em>bis</em>-phosphine ligands with different chelating groups has been documented. A brief alkyne and alkene component scope is also included.</p> <br/><p align="center"><img alt="Figure.3" src="https://ora.ox.ac.uk/objects/uuid:1bea588d-c54e-429a-8e12-66de38ffb3ad/datastreams/content04" style="width:364px;height:132px;"/></p><br/> <p>Chapter 5 documents the experimental data.</p> <p>Appendix presents <sup>1</sup>H, <sup>13</sup>C and <sup>19</sup>F NMR spectra of novel compounds and chiral HPLC data.</p> |
| spellingShingle | Niu, J Development and applications of rhodium-catalysed reactions to explore the synthesis of heterocycles |
| title | Development and applications of rhodium-catalysed reactions to explore the synthesis of heterocycles |
| title_full | Development and applications of rhodium-catalysed reactions to explore the synthesis of heterocycles |
| title_fullStr | Development and applications of rhodium-catalysed reactions to explore the synthesis of heterocycles |
| title_full_unstemmed | Development and applications of rhodium-catalysed reactions to explore the synthesis of heterocycles |
| title_short | Development and applications of rhodium-catalysed reactions to explore the synthesis of heterocycles |
| title_sort | development and applications of rhodium catalysed reactions to explore the synthesis of heterocycles |
| work_keys_str_mv | AT niuj developmentandapplicationsofrhodiumcatalysedreactionstoexplorethesynthesisofheterocycles |