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Novel Main Group Lewis Acids for Synthetic and Catalytic Transformations

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Novel Main Group Lewis Acids for Synthetic and Catalytic Transformations Novel main group Lewis acids for synthetic and catalytic transformations Yashar Soltani A thesis submitted to Cardiff University in candidature for the degree of Doctor of Philosophy Department of Chemistry, Cardiff University September 2018 DECLARATION This work has not been submitted in substance for any other degree or award at this or any other university or place of learning, nor is being submitted concurrently in candidature for any degree or other award. Signed ………………………………………… (candidate) Date ……………………… STATEMENT 1 This thesis is being submitted in partial fulfillment of the requirements for the degree of PhD. Signed ………………………………………… (candidate) Date ………………………… STATEMENT 2 This thesis is the result of my own independent work/investigation, except where otherwise stated. Other sources are acknowledged by explicit references. The views expressed are my own. Signed ………………………………………… (candidate) Date ………………………… STATEMENT 3 I hereby give consent for my thesis, if accepted, to be available for photocopying and for inter-library loan, and for the title and summary to be made available to outside organisations. Signed ………………………………………… (candidate) Date ………………………… I Acknowledgements I am very grateful to my supervisor Dr Rebecca Melen for the opportunity to work in her group and for her continued advice and guidance over the past three years. Thanks, must also be given to all the members of the Melen group. To Dr James Lawson as well as Dr Adam Ruddy for helping me to overcome scientific challenges. Also, Jamie Carden must be thanked here for his support in correcting the thesis, as well as all the other current and former members of the Melen group for many happy memories. I would also like to extend my gratitude to Prof. Oestreich for hosting my research stay in Berlin at the TU Berlin. My gratitude is also due to all the professional services staff at Cardiff University; especially Dr Rob Jenkins, Simon Waller, Tom Williams, Evelyn Blake and Jamie Cross. I am also especially grateful to the following people for their collaborative assistance throughout this thesis: Prof Simon Pope, Dr Paul Newman, Jenny Börger, Vladimir Y. Vladimirov, Dale Lyons and Theo A. Gazis. I am specifically appreciative to Dr Lewis C. Wilkins for his assistance in the reactions of alkynyl acids and esters with tris(pentafluorophenyl)borane. Here he did the cyclisation reactions in Scheme 58 and the reactions to give compound 5.16a and 5.16b in Scheme 64. He also conducted the catalytic reactions to give 5.17a, b, f & g in Scheme 65. In Chapter 7 he did the haloboration reaction to give 7.2c in Scheme 97 and the carboboration reaction to give 7.3c in Scheme 98. He also collected X-ray data and solved/refined crystal structures of compounds 1h and 1i in Figure 2, 1l in Figure 3, 4.4a in Figure 10, 5.4c & 5.16a in Figure 22, 7.2d in Figure 31 and 7.3a in Figure 32. I am also appreciative to Dr Sam J. Adams for the photophysical studies of imine borane adducts in Chapter 4, Dr Emma Richards for the electron paramagnetic resonance spectroscopic measurements in Chapter 6, Prof Qin Yin for guidance in the hydroboration reactions in Chapter 3 and Darren M. C. Ould for solving crystal structures of compound 1n in Figure 3, 6.2a in Figure 24 and 6.2b in Scheme 77. On a personal note, I am indebted to my family for their unfailing support, to my sister for never failing to cheer me up, and my mother and my father for their continuous believe in me. I want to thank my friends for understanding that a lack of time in some instances does not mean a loss of interest. I II Abstract The work described herein is concerned with Lewis acidic triarylboranes for synthetic and catalytic transformations where the influence of different substitution pattern and substituents were crucial in determining the resulting reactivity. Chapter 1 will provide a general introduction into acidity and will lay the theoretical foundation for the ensuing chapters. Chapter 2 introduces the boranes utilised in this work and will give literature examples describing reactivities of the currently known boranes. Besides providing several crystal structures, this chapter will discuss the Lewis acidity of these boranes. Chapter 3 explores the hydroboration of imines catalysed by tris[3,5-bis(trifluoromethyl)- phenyl]borane. By testing a variety of various Lewis acids further insight into the mechanism of this hydroboration is gained. Chapter 4 further investigates borane imine adducts and the impact of the adduct formation on the electronic transitions within the imines. The photoactive adducts are then explored as vapochromic materials towards various solvent vapours. Chapter 5 focuses on the formation of pyrones, dihydropyrones and isocoumarins catalysed by tris(pentafluorophenyl)borane. A cross over experiment reveals the nature of this cyclisation reaction. Chapter 6 investigates the radical character of a frustrated Lewis pairs and their resulting reactivity. A novel protocol for a radical Heck-type reaction is provided and the mechanism was investigated. Finally, Chapter 7 will show the ambiguity between 1,1-carboboration and 1,3-haloboration in the reaction of propargyl esters with dichlorophenylborane. II Contents I Acknowledgements ................................................................................................................... I II Abstract .................................................................................................................................... II III List of publications ................................................................................................................ VI IV List of abbreviations ............................................................................................................ VII 1 General introduction ............................................................................................................... 1 1.1 Lewis acids ....................................................................................................................... 1 1.2 The Gutmann Beckett method ....................................................................................... 2 1.3 Reactivity of Lewis acids ................................................................................................ 3 1.4 Lewis acidic boron compounds ..................................................................................... 4 1.5 Frustrated Lewis pairs ..................................................................................................... 6 2 Introduction of the boranes synthesised in this work ....................................................... 10 2.1 Tris(pentafluorophenyl)borane ..................................................................................... 10 2.2 Tris[3,5-bis(trifluoromethyl)phenyl]borane ................................................................. 14 2.3 Tris(3,4,5-trifluorophenyl)borane ................................................................................. 15 2.4 Tris(2,4,6-trifluorophenyl)borane ................................................................................. 16 2.5 Tris(3,4-dichlorophenyl)borane & tris(4-fluorophenyl)borane ................................. 17 2.6 Summary ......................................................................................................................... 18 3 Hydroboration of ketimines .................................................................................................. 20 3.1 Introduction ..................................................................................................................... 20 3.2 Aims of this work ............................................................................................................ 23 3.3 Results ............................................................................................................................ 23 3.4 Summary & Outlook ...................................................................................................... 28 4 Photophysical studies of B(C6F5)3 imine adducts ............................................................. 29 4.1 Introduction ..................................................................................................................... 29 4.2 Aims of this work ............................................................................................................ 30 4.3 Synthetic results ............................................................................................................. 30 4.4 Photophysical results .................................................................................................... 33 4.5 Vapochromic results ...................................................................................................... 39 4.6 Discussion of vapochromic results .............................................................................. 40 4.7 Summary & Outlook ...................................................................................................... 41 5 B(C6F5)3 promoted cyclisation of substituted alkynyl esters, ethers, and acids ........... 43 5.1 Introduction ..................................................................................................................... 43 5.2 Aim of this work .............................................................................................................. 48 5.3 Synthesis of the starting material and their reaction with B(C6F5)3 ........................ 48 5.4 Results
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