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Vronaldson Thesis May09.Pdf (5.506Mb) Active Template Strategies for the Assembly of Mechanically Interlocked Molecules Vicki E. Ronaldson Degree of Doctor of Philosophy School of Chemistry University of Edinburgh May 2009 Vicki E. Ronaldson, 2009 2 Vicki E. Ronaldson, 2009 Dedicated to my Family i Vicki E. Ronaldson, 2009 Table of Contents Abstract ...................................................................................................................iv Declaration ............................................................................................................... v Conferences and Meetings Attended ......................................................................vi Acknowledgements...............................................................................................viii List of Abbreviations ............................................................................................viii General Comments on Experimental Data............................................................... x Thesis Layout..........................................................................................................xi Chapter 1: Introduction to the Templated Assembly of Mechanically Interlocked Molecules................................................................................................ 1 1.1 Mechanical Bonds and Interlocked Molecules ............................................ 2 1.2 Histrory and Early Synthetic Attempts ........................................................ 3 1.3 Template-Directed Synthesis ....................................................................... 4 1.3.1 Transition Metal Templates ................................................................ 5 1.3.2 Non-Transition Metal Templates ...................................................... 13 1.3.3 The Active Template Strategy .......................................................... 19 Chapter 2: A Cu(I)-Catalyzed Azide-Alkyne 1,3-Cycloaddition Active Template Reaction..................................................................................................................... 22 2.1 Introduction................................................................................................ 23 2.2 Results and Discussion............................................................................... 27 2.2 Experimental .............................................................................................. 45 Chapter 3: A Nickel-Copper-Mediated Alkyne Homocoupling Active Template ................................................................................................................... 63 3.1 Introduction................................................................................................ 64 3.2 Results and Discussion............................................................................... 67 3.3 Experimental .............................................................................................. 79 ii Vicki E. Ronaldson, 2009 Chapter 4: Doubly-Threaded [3]Rotaxanes from a Single Active Template Binding Site............................................................................................................... 86 4.1 Introduction................................................................................................ 87 4.2 Results and Discussion............................................................................... 90 4.3 Experimental .............................................................................................. 98 Chapter 5: Towards Active Template Carbene Transformations .................... 118 5.1 Introduction.............................................................................................. 119 5.2 Results and Discussion............................................................................. 121 5.3 Experimental ............................................................................................ 133 References and Notes ............................................................................................. 142 Appendix 1: Published Work................................................................................ 157 iii Vicki E. Ronaldson, 2009 Abstract Chemical templates have allowed the synthesis of increasingly complex mechanically interlocked molecular architectures. Transition metals are useful templating agents. Their coordination requirements result in the well-defined, three- dimensional orientation of reactive fragments. Judicious choice of ligand and metal leads to a mechanically interlocked product upon covalent bond formation between the fragments. In such ‘passive’ templates a stoichiometric quantity of metal, with respect to the reacting components, is required. The metal atom acts as ‘glue’ until covalent, and consequent mechanical, bond formation has occurred. Recently in the Leigh group a fundamentally novel approach to interlocked architectures has been discovered and takes its cue from transition metal catalysis: in addition to inducing the necessary degree of preorganization in the system, the metal also mediates the covalent bond formation. This thesis describes further investigation of the original active template reaction—a ‘click’ reaction—and the subsequent extension of the strategy to new reactions and architectures. The effect of varying the macrocyclic ligand on the original Cu(I)-catalyzed 1,3- dipolar cycloaddition between alkynes and azides was investigated. Notably, the interlocked nature of the products provided new mechanistic insights into the nature of this widely used reaction. Following this, a Ni(II) active template was developed for the homocoupling of terminal alkynes. An unusual Ni/Cu system for this reaction was discovered and the resulting [2]rotaxanes were produced in excellent yield. The utility of the active template strategy was further demonstrated by the synthesis of a [3]rotaxane from a bifurcated macrocycle with a pyridyl bridging unit. Cu(I) catalyzed the formation of a triazole thread through each cavity, showing that multiple mechanical bonds can be formed from a single active template binding site. Lastly, the potential of carbene transfer reactions in the active template approach was investigated. A stoppered diazoester compound was synthesized and used in studies towards X-H insertion and cycloaddition reactions in the presence of a range of macrocyclic ligands iv Vicki E. Ronaldson, 2009 Declaration The scientific work described in this thesis was carried out in the School of Chemistry at the University of Edinburgh between September 2005 and September 2008. Unless otherwise stated, it is the work of the author and has not been submitted in whole or in support of an application for another degree or qualification of this or any other University or institute of learning. Signed…..………………………………. Date………………………… v Vicki E. Ronaldson, 2009 Conferences and Meetings Attended 1. Scottish Organic and Biomolecular Chemistry meeting, University of Aberdeen, UK, 12/08. 2. Organic Research Seminars, University of Edinburgh, UK, 2005-2008. 3. Scottish Chemical Industries Postgraduate Symposium, University of Strathclyde, UK, 04/08. 20 minute oral presentation entitled ‘Active Template Strategies for the Synthesis of Mechanically Interlocked Architectures’. 4. Scottish Organic and Biomolecular Chemistry meeting, University of Glasgow, Scotland, 12/07. Poster entitled ‘An Unusual Ni/Cu Bimetallic Active Template Reaction for the Synthesis of [2]Rotaxanes.’ 5. Organon Synthetic Chemistry Symposium, University of Glasgow, UK, 10/07. Poster entitled ‘An Unusual Ni/Cu Bimetallic Active Template Reaction for the Synthesis of [2]Rotaxanes.’ 6. International Symposium on Macrocyclic and Supramolecular Chemistry, Salice Terme, Italy, 07/07. Poster entitled ‘An Unusual Ni/Cu Bimetallic Active Template Reaction for the Synthesis of [2]Rotaxanes.’ 7. The Young(-ish!) Giants of Chemistry Symposium, University of Edinburgh, UK, 06/07. Poster entitled ‘An Unusual Ni/Cu Bimetallic Active Template Reaction for the Synthesis of [2]Rotaxanes.’ 8. Scottish Organic and Biomolecular Chemistry meeting, University of Strathclyde, 12/05. vi Vicki E. Ronaldson, 2009 Acknowledgements I would firstly like to thank my supervisor, Prof. David Leigh, for giving me the opportunity to carry out the research described in this thesis. Special thanks to Dr. Stephen Goldup for his invaluable guidance over the last three years, as well as proofreading this thesis. Thank you! Thanks to Dr. Bryan Koivisto for his fantastic proofreading service and many words of wisdom. I would also like to thank the following people for their advice and practical input during the course of my PhD: Dr James Crowley, Dr Vincent Aucagne, Dr José Berna, Dr Satoshi Nakamura, Paul McGonigal and Nick Gowans. The research described would not have been possible without the fantastic technical support I have received over the last three years, for which I would like to thank: Diego Gonzales, Mark Symes, Paul McGonigal and Max Von Delius, for keeping all things NMR running smoothly; Alan Taylor, for a first class mass spectrometry service; Prof. Alexandra Slawin for solving crystal structures and Stewart Franklin and Louise Hogg for synthesizing some starting materials, saving me countless lab hours by doing so. I have to thank Vince, Pepe, Bryan, Steve, Kevin, Max, Edzard, Marius, Nick, Takeshi, and Anthony for making the west bay the best bay; even though my balance cleaning rota went largely ignored! Thanks to Amaya, Kev, Marius, Max and
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