The development of novel gold-catalysed indole cascade reactions

• Main Author: Heffernan, Stephen John
• Other Authors: Carbery, David
• Published: University of Bath 2012
• Subjects: 547.2
• Online Access: https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.557812

Divided into three distinct research areas, this thesis investigates the synthetic utility of enynones and ynamides towards the formation of biologically relevant structures. The first volume of work (Chapter 2) describes the gold-catalysed double alkylation of indole by enynones. The [6,5,7]-tricycles formed in this reaction are generally provided in excellent yield with complete regioselectivity. Optimisation of the procedure, a thorough substrate investigation, and mechanistic insights are discussed within. The gold-catalysed rearrangement of ynamido esters is described in Chapter 3. Following 1,3-acyl transfer, nucleophilic addition of indole to the intermediate allenamide provides a novel enamide scaffold. The substrate scope has been assessed, with high yields provided for most examples. The final chapter concerns the Ireland-Claisen rearrangement of ynamido esters, with post-rearrangement decarboxylation furnishing aminodienes. Following a substantial optimisation study, a range of ynamido esters were screened, providing a range of functionalised aminodienes in good yield with varying Z:E selectivity.