In this thesis, the construction of the allylic fluorides under palladium catalysis was investigated. 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. In Chapter 2 the identification that a p-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(tBuOH)<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, E- and Z-linear allylic fluorides in a regioselective manner. This methodology was also translated to <sup>18</sup>F radiochemistry. In Chapter 3 the synthesis of allylic fluorides via 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. 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. Chapter 5 gives full experimental procedures and characterization data for all compounds.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:669891 |
| Date | January 2013 |
| Creators | Hollingworth, Charlotte |
| Contributors | Gouverneur, Véronique |
| Publisher | University of Oxford |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://ora.ox.ac.uk/objects/uuid:8c61b9e9-b143-4c5e-b151-7e62bf4ecc03 |
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