Leigh, David A.

Hänni, Kevin D.

2010-10-04T09:10:57Z

2010-10-04T09:10:57Z

2009

In contrast to the classic ‘passive template’ approach, an ‘active-metal’ template strategy involves a metal centre which acts as both a template and the catalyst for covalent bond formation in the construction of mechanically interlocked architectures. The crucial formation of a covalent bond between two ‘half-threads’ is promoted by the catalyst and directed through the cavity of the macrocycle by the catalyst’s coordination requirements. The main attractive features of such a synthetic approach are the efficiency (as one step is required instead of two), the rapid assembly of inaccessible structures, the possibility of ‘traceless’ assemblies, the versatility, the possibility to use catalytic amount of the metal template and to provide mechanistic insight. This novel concept was successfully introduced by our group and applied to a wide range of well-known transition metal-catalysed reactions. The thesis will present several examples of active-metal template reactions for the synthesis of interlocked architectures, including Cu(I)-catalysed alkyne-azide cycloaddition (CuAAC popularised as the click reaction), Pd(II)-catalysed alkyne homocouplings Pd(II)-catalysed oxidative Heck cross-couplings and Lewis acids mediated Diels-Alder reactions.

http://hdl.handle.net/1842/3802

en

The University of Edinburgh

Part of the work presented in sections 2.3.1, 2.3.2 and 2.3.6 (Chapter II) has been submitted for a MSc degree in Molecular and Biological Chemistry at the Ecole Polytechnique Fédérale de Lausanne (Switzerland) in December 2005.

transition metal-catalysed reactions

active-metal template reactions

interlocked architectures

Heck cross-couplings

Mechanically interlocked architectures via active-metal template strategies

Thesis or Dissertation

Doctoral

PhD Doctor of Philosophy