Palladium mediated allylic fluorination
<p>In this thesis, the construction of the allylic fluorides under palladium catalysis was investigated.</p> <p>Chapter 1 provides a general introduction to organofluorine compounds and the use of palladium for the formation of both Csp<sup>2</sup>- and Csp<sup>3&...
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| Natura: | Tesi |
| Lingua: | English |
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2013
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| _version_ | 1826312256984449024 |
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| author | Hollingworth, C |
| author2 | Gouverneur, V |
| author_facet | Gouverneur, V Hollingworth, C |
| author_sort | Hollingworth, C |
| collection | OXFORD |
| description | <p>In this thesis, the construction of the allylic fluorides under palladium catalysis was investigated.</p> <p>Chapter 1 provides a general introduction to organofluorine compounds and the use of palladium for the formation of both Csp<sup>2</sup>- and Csp<sup>3</sup>-F bonds. The aims of the thesis are presented.</p> <p>In Chapter 2 the identification that a <em>p</em>-nitrobenzoate is the optimum leaving group under Pd-catalysis to give allyl fluorides is described. A range of allylic fluorides was synthesized in 35->95% yield using the nucleophilic fluorinating reagent, TBAF(<em>t</em>BuOH)<sub>4</sub>. To further develop this transformation we have examined the effect of a variety of leaving groups and phosphine ligands. This methodology led to the development of the first transition metal mediated C-<sup>18</sup>F bond formation. The development of Ir-catalysed fluorination of allylic carbonates to give allylic fluorides is also discussed. This system provided access to branched, <em>E</em>- and <em>Z</em>-linear allylic fluorides in a regioselective manner. This methodology was also translated to <sup>18</sup>F radiochemistry.</p> <p>In Chapter 3 the synthesis of allylic fluorides <em>via</em> a C-H functionalisation with Pd and nucleophilic source of fluorine was investigated. Comprehensive screening of Pd sources, fluoride reagents and additives was performed. The presence of a quinone was found to be crucial for this transformation.</p> <p>Chapter 4 describes the synthesis and characterization of a series of allylpalladium(II) complexes and their subsequent reactivity towards a range of electrophilic fluorination reagents.</p> <p>Chapter 5 gives full experimental procedures and characterization data for all compounds.</p> |
| first_indexed | 2024-03-07T08:24:52Z |
| format | Thesis |
| id | oxford-uuid:8c61b9e9-b143-4c5e-b151-7e62bf4ecc03 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T08:24:52Z |
| publishDate | 2013 |
| record_format | dspace |
| spelling | oxford-uuid:8c61b9e9-b143-4c5e-b151-7e62bf4ecc032024-02-13T16:57:17ZPalladium mediated allylic fluorinationThesishttp://purl.org/coar/resource_type/c_db06uuid:8c61b9e9-b143-4c5e-b151-7e62bf4ecc03Physical SciencesOrganic chemistryOrganometallic ChemistryChemistry & allied sciencesOrganic synthesisEnglishOxford University Research Archive - Valet2013Hollingworth, CGouverneur, V<p>In this thesis, the construction of the allylic fluorides under palladium catalysis was investigated.</p> <p>Chapter 1 provides a general introduction to organofluorine compounds and the use of palladium for the formation of both Csp<sup>2</sup>- and Csp<sup>3</sup>-F bonds. The aims of the thesis are presented.</p> <p>In Chapter 2 the identification that a <em>p</em>-nitrobenzoate is the optimum leaving group under Pd-catalysis to give allyl fluorides is described. A range of allylic fluorides was synthesized in 35->95% yield using the nucleophilic fluorinating reagent, TBAF(<em>t</em>BuOH)<sub>4</sub>. To further develop this transformation we have examined the effect of a variety of leaving groups and phosphine ligands. This methodology led to the development of the first transition metal mediated C-<sup>18</sup>F bond formation. The development of Ir-catalysed fluorination of allylic carbonates to give allylic fluorides is also discussed. This system provided access to branched, <em>E</em>- and <em>Z</em>-linear allylic fluorides in a regioselective manner. This methodology was also translated to <sup>18</sup>F radiochemistry.</p> <p>In Chapter 3 the synthesis of allylic fluorides <em>via</em> a C-H functionalisation with Pd and nucleophilic source of fluorine was investigated. Comprehensive screening of Pd sources, fluoride reagents and additives was performed. The presence of a quinone was found to be crucial for this transformation.</p> <p>Chapter 4 describes the synthesis and characterization of a series of allylpalladium(II) complexes and their subsequent reactivity towards a range of electrophilic fluorination reagents.</p> <p>Chapter 5 gives full experimental procedures and characterization data for all compounds.</p> |
| spellingShingle | Physical Sciences Organic chemistry Organometallic Chemistry Chemistry & allied sciences Organic synthesis Hollingworth, C Palladium mediated allylic fluorination |
| title | Palladium mediated allylic fluorination |
| title_full | Palladium mediated allylic fluorination |
| title_fullStr | Palladium mediated allylic fluorination |
| title_full_unstemmed | Palladium mediated allylic fluorination |
| title_short | Palladium mediated allylic fluorination |
| title_sort | palladium mediated allylic fluorination |
| topic | Physical Sciences Organic chemistry Organometallic Chemistry Chemistry & allied sciences Organic synthesis |
| work_keys_str_mv | AT hollingworthc palladiummediatedallylicfluorination |