Synthesis and reactivity of allylic fluorides under transition metal catalysis

Thesis

In this thesis, C-F bond activation and C-F bond construction under platinum and iridium catalysis is described.

Chapter 1 provides a general introduction on the use of transition metal catalysis for the formation and activation of Csp³-F bonds in organofluorine compounds.

In Chapter 2, an investigation on the reactivity of allylic fluorides, under platinum and palladium catalysed alkylation conditions, is presented. The relative reactivity of fluoride versus other commonly used leaving groups was compared via internal competition experiments. Fluoride showed a different reactivity profile, when subjected to Pt and Pd catalytic systems. Based on the observed reactivity trend, a Pd-catalysed fluorination reaction of allylic alcohol derivatives was successfully developed, within the group.

In Chapter 3, a new iridium catalysed fluorination using branched, E- or Z-linear allylic carbonates is described. The catalyst [Ir(COD)Cl]₂ leads to an unexpected regio- and stereoretentive selectivity, affording fluorinated products not accessible via palladium catalysis. The effect of a fluoride additive on the selectivity of the Ir-catalysed alkylation reaction is also presented. A highly efficient ¹⁸F-fluorination variant for this new catalytic transformation is reported.

Chapter 4 gives full experimental procedures and characterisation data for all compounds.

Authors: Benedetto, E

• Publication date: 2013
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Keywords: organometallic catalysis; fluorine chemistry
• Subjects: Organic chemistry