Rollover in the synthesis of polycyclic indoles, and a one-pot Zipper-Click reaction

Abstract

This thesis contains two chapters, the first concerning the use of C-H activation in the synthesis of polyaromatic indoles, and the second concerning an investigation into the acetylene zipper reaction.C-H activation provides a convenient, atom efficient route for the construction of C-C bonds, without the prerequisite for stoichiometric organometallic precursors or pre-functionalisation of the substrates. In this research the use of C-H activation for the insertion of an alkyne into an N-(hetero)arylated indole system has been investigated; the transformation was achieved using Rh catalysis in moderate to good yields. The concept of rollover has also been discussed. This is where, after a metallation step, the molecule undergoes a bond rotation allowing further reaction at a different part of the molecule.The acetylene zipper reaction is a powerful contrathermodynamic reaction which allows the migration of an internal alkyne to the terminal position. The alkyne moiety is a useful handle for many reactions, not least the robust CuI-catalysed azide alkyne cycloaddition (CuAAC, also known as a click reaction), which can be used to synthesis useful triazole products. In this research a one-pot zipper-click reaction has been investigated to provide 1,4-disubstituted-1,2,3-triazoles.

Date of Award	1 Aug 2016
Original language	English
Awarding Institution	The University of Manchester
Supervisor	Peter Quayle (Supervisor) & Michael Greaney (Supervisor)