This thesis investigates the use of aluminium trichloride and acetyl chloride to functionalise saturated hydrocarbons and probe the mechanism by which this functionalisation occurs. It also looks at the use of iridium catalysis to form carbon-boron bonds from carbon-hydrogen bonds in naphthalenediimides or NDIs.Chapter one reviews work published in the field of carbon-hydrogen bond functionalisation; from the traditional reactions of hydrocarbons as simple as combustion to cutting-edge selective C-H activation in natural product synthesis.Chapter two investigates experimentally the mechanism of the “Baddeley reaction”; the low-temperature interaction of decalin with aluminium trichloride and acetyl chloride, identifying key intermediates on the mechanistic pathway and the order of reaction in acylating reagent and substrate.Chapter three applies the Baddeley methodology to other saturated hydrocarbons, selected for certain commonalities with decalin based on the mechanism established. The results of these reactions include unusual sketetal rearrangements and the synthesis of novel compounds.Chapter four focuses on C-H borylation of NDIs at the naphthalene core; optimisation of the reaction uses microwave heating and both mono-borylated and di-borylated isomers can be synthesised. These boronic esters formed are suitable starting materials for further reactions; examples of possible Suzuki reactions are detailed. Chapter five details experimental procedures associated with the work of the previous three chapters.
|Date of Award||29 May 2014|
|Supervisor||Simon Lewis (Supervisor)|