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Title: Palladium mediated allylic fluorination
Author: Hollingworth, Charlotte
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2013
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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 Csp2- and Csp3-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)4. 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-18F 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 18F 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.
Supervisor: Gouverneur, Véronique Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Chemistry & allied sciences ; Organic chemistry ; Organic synthesis ; Organometallic Chemistry ; Physical Sciences ; Palladium ; fluorine ; catalysis ; allylic