The development of gold-catalysed reactions

Abstract

This thesis describes the research carried out in the development of novel homogeneous gold(I)-catalysed reactions. It is written in such a format as to describe chronologically the process in which the study and our understanding evolved. Chapter one provides an introduction to homogeneous gold catalysis and in particular the development and reactivity of gold(I) catalysts as powerful activators of unsaturated carbon-carbon species towards nucleophilic attack. Chapter two describes our initial work in this area and how we were able to show that gold(I) can catalyse the intramolecular rearrangements of cyclopropenes with ester functionalities. Chapter three presents the intermolecular addition of alcohol to 3,3-dialkyl and aryl cyclopropenes catalysed by gold(I). Chapter four describes how we were able to utilise our knowledge of gold(I)-catalysed reactions with cyclopropenes to completely switch the regiochemistry of gold(I)-catalysed hydroalkoxylation of allenes from producing primary alkyl allylic ethers to tertiary alkyl allylic ethers. We were also able to show that by trapping the vinyl gold intermediate we could further functionalise the tertiary allylic ether. Chapter five describes the results of the addition of furan to cyclopropenes catalysed by gold(I) to produce functionalised conjugated trienes. Chapter six presents initial work into the gold(I) catalysed addition of indoles to cyclopropenes. Also described in this chapter are the attempted reactions with a variety of alternative nucleophiles.