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Thesis Style Document Studies Towards the Asymmetric Synthesis of Cyclochiral Rotaxanes and Au(III)-oxo Complexes as Catalysts James Alan Thomas O’Neill Submitted for the degree of Doctor of Philosophy Heriot-Watt University School of Engineering and Physical Sciences April 2015 The copyright in this thesis is owned by the author. Any quotation from the thesis or use of any of the information contained in it must acknowledge this thesis as the source of the quotation or information. ABSTRACT The work reported in this thesis consists of studies towards the asymmetric synthesis of mechanically planar chiral rotaxanes via desymmetrisation approach. It describes the synthesis of a novel macrocycle and the investigation of this macrocycle as a potential ligand in the Cadiot-Chodkiewicz and CuAAC ‘click’ reactions as part of the study towards the synthesis of asymmetric planar chiral rotaxanes. Furthermore, the use of Au(III)-oxo complexes as potential catalysts in a model hydroamination reaction are described. The thesis is divided into four chapters: Chapter one is an introduction to rotaxanes and includes an overview of the synthesis of rotaxanes and chirality in rotaxanes. Chapter two is an account of the synthesis of a novel macrocycle and details attempts to implement this macrocycle towards the synthesis of a rotaxane using the Cadiot- Chodkiewicz and CuAAC ‘click’ reactions. Chapter three describes optimisation and multi-gram scale-up of the synthetic route towards a novel C1-symmetric bis(oxazoline) macrocycle first synthesised in our group by Pauline Glen. Chapter four describes our investigation into the use of Au(III)-oxo complexes for use as catalysts in a model hydroamination reaction. i DEDICATION I would like to dedicate this work to my wife, Andrea. ii ACKNOWLEDGEMENTS First and foremost, I would like to thank Ai-Lan for the opportunity to work in the Lee group on what has been a challenging project and for all the support, advice and endless patience you have given me throughout my studies and the writing process. Thanks to Pauline, Paul, Jamie, Sarah, Mari and Robert who have all provided support, guidance and continued friendship. I would like to thank all the staff in the chemistry department at Heriot-Watt for the expertise they have passed on and for all the support throughout all the years I have been here. In particular, thank you to the members of the organic chemistry section who have provided invaluable help throughout this project and to Alan Boyd and Georgina Rosair for their guidance around NMR and Single Crystal X-Ray Diffraction. Special thanks also go to Christina Graham for all her help throughout my time at Heriot-Watt. Thanks go to the EPSRC for providing the funding for this project. Last, but not least, a big thank you to my family. Andrea, thank you for your love, support and encouragement throughout this work. Without it, I wouldn’t have got there. To my Mum and Dad, thank you for always pushing me to achieve the best I can in life. I will always be grateful for your sacrifices over the years. iii ACADEMIC REGISTRY Research Thesis Submission Name: James Alan Thomas O’Neill School/PGI: School of Engineering and Physical Sciences Version: (i.e. First, Final Degree Sought Doctor of Philosophy Resubmission, Final) (Award and Chemistry Subject area) Declaration In accordance with the appropriate regulations I hereby submit my thesis and I declare that: 1) the thesis embodies the results of my own work and has been composed by myself 2) where appropriate, I have made acknowledgement of the work of others and have made reference to work carried out in collaboration with other persons 3) the thesis is the correct version of the thesis for submission and is the same version as any electronic versions submitted*. 4) my thesis for the award referred to, deposited in the Heriot-Watt University Library, should be made available for loan or photocopying and be available via the Institutional Repository, subject to such conditions as the Librarian may require 5) I understand that as a student of the University I am required to abide by the Regulations of the University and to conform to its discipline. * Please note that it is the responsibility of the candidate to ensure that the correct version of the thesis is submitted. Signature of Date: Candidate: Submission Submitted By (name in capitals): ANDREA MCVITTIE Signature of Individual Submitting: Date Submitted: For Completion in the Student Service Centre (SSC) Received in the SSC by (name in capitals): Method of Submission (Handed in to SSC; posted through internal/external mail): E-thesis Submitted (mandatory for final theses) Signature: Date: iv TABLE OF CONTENTS ABSTRACT ..................................................................................................................... I DEDICATION ................................................................................................................ II ACKNOWLEDGEMENTS ......................................................................................... III TABLE OF CONTENTS ............................................................................................... V ABBREVIATIONS ..................................................................................................... VII CHAPTER 1 – INTRODUCTION ................................................................................ 1 1.1 Mechanically Interlocked Molecular Architectures ........................................... 1 1.2 Nomenclature of Rotaxanes ............................................................................... 1 1.3 Applications of Molecular Interlocked Architectures ........................................ 2 1.4 Overview of Classical Synthetic Methodologies of Rotaxanes ......................... 6 1.4.1 Early Statistical Approaches ....................................................................... 7 1.4.2 Directed Synthesis by Covalent Bond Formation ....................................... 7 1.4.3 Cyclodextrin Mediated Template Synthesis ............................................... 8 1.4.4 Hydrogen Bond Mediated Templating........................................................ 9 1.4.5 π-electron donor/π-electron acceptor interactions ..................................... 12 1.4.6 Transition Metal Templating .................................................................... 13 1.5 Active Metal Template Synthesis of Rotaxanes ............................................... 14 1.5.1 CuAAc Active Metal Template For Rotaxane Synthesis ......................... 16 1.5.2 Copper Mediated Oxidative Alkyne-Alkyne Homocoupling ................... 17 1.5.3 Copper Mediated Alkyne-Alkyne Heterocoupling ................................... 19 1.5.4 Palladium(II)-Catalysed Active Metal Template Reactions ..................... 20 1.6 Cyclochirality and Rotaxanes ........................................................................... 23 CHAPTER 2 – STUDIES TOWARDS THE SYNTHESIS OF A CYCLOCHIRAL ROTAXANE .................................................................................................................. 25 2.1 Results and Discussion ..................................................................................... 25 2.1.1 Project Overview ....................................................................................... 25 2.1.2 Design of a Prochiral Rotaxane for Desymmetrisation............................. 25 2.1.3 Synthetic overview of the target prochiral rotaxane ................................. 26 2.2 Preparation of Macrocycle 2.1 ......................................................................... 27 2.3 Synthesis of Macrocycle Precursor 2.22 .......................................................... 30 2.4 Preparation of Macrocycle 2.26 ....................................................................... 35 2.5 Synthesis of Macrocycle Precursor 2.27 .......................................................... 36 2.6 Synthesis of Macrocycle Precursor 2.28 .......................................................... 40 2.7 Preparation of Macrocycle Precursor 2.43 ....................................................... 43 2.8 Synthesis of Macrocycle 2.42 .......................................................................... 45 2.9 Cadiot-Chodkiewicz Heterocoupling Reaction ................................................ 46 2.9.1 Introduction ............................................................................................... 46 2.9.2 Cadiot-Chodkiewicz in Supramolecular Chemistry.................................. 47 2.9.3 Synthesis of Stoppers for the Cadiot-Chodkiewiz Reaction ..................... 48 2.10 Cadiot-Chodkiewicz Reaction Results ............................................................. 49 2.11 Conclusion ........................................................................................................ 50 v 2.12 CuAAC ‘Click’ Reaction ................................................................................. 52 2.12.1 Introduction ............................................................................................... 52 2.12.2 CuAAC ‘Click’ Reaction in Supramolecular Chemistry .......................... 52 2.12.3 Investigation of the use of the CuAAC ‘Click’ Reaction for Rotaxane Formation ................................................................................................................. 52 2.12.4 Synthesis of Suitable Rotaxane Stoppers for a CuAAC ‘click’ Reaction . 53 2.13 CuAAC Reaction Results ................................................................................
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