In this thesis, the effect of fluorinating reagents on a selection of transition metal-mediated organic transformations was investigated. The first four chapters are focused on gold-catalysed nucleophilic addition processes performed in the presence of “F⁺” sources. Chapter 1 provides a general introduction to homogeneous gold catalysis and summarises the aims and objectives of the project. The effect of the electrophilic fluorinating reagent Selectfluor (82) on the gold-catalysed rearrangement of propargyl acetates 85 is discussed in Chapter 2. α-Fluoroenones 92 resulting from fluorodeacetylation of an allenyl acetate intermediate were delivered as the major products of these reactions (Scheme i). [Scheme i Gold-Catalysed Rearrangement-Fluorodeacetylation of Propargyl Acetates 85.] By contrast, performing the gold(I)-catalysed cyclisation of allenoates 102 in the presence of Selectfluor (82) led to products of oxidative coupling. The “F⁺” source in these processes most likely acts as an external oxidant in an Au<sup>I</sup</Au<sup>III</sup> redox cycle. In Chapter 3, the cascade cyclisation-intramolecular arylation of benzyl-substituted substrates is discussed whilst the extension of the methodology towards intermolecular homocoupling and intermolecular alkynylation is presented in Chapter 4 (Scheme ii). [Scheme ii Gold-Catalysed Cyclisation-Oxidative Coupling of tert-Butyl Allenoates 102.] In Chapter 5, the feasibility of palladium-catalysed allylic [<sup>18</sup>F]radiofluorination was investigated using high-specific-activity [<sup>18</sup>F]fluoride. This study led to the development of the first transition metal-mediated C-<sup>18</sup>F bond-forming process of relevance for the preparation of radiotracers for PET imaging (Scheme iii). [Scheme iii Palladium-Catalysed Allylic [18F]Radiofluorination of Allylic Methyl Carbonate 227b.] Chapter 6 gives full experimental procedures and characterisation data for all compounds.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:558388 |
| Date | January 2011 |
| Creators | Hopkinson, Matthew Neil |
| 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:4f29607a-7aad-473b-aabc-af320ea2b1e5 |
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