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Borenium Cations for the Direct Electrophilic Borylation of Arenes 2012 Alessandro Del Grosso School of Chemistry

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Borenium Cations for the Direct Electrophilic Borylation of Arenes 2012 Alessandro Del Grosso School of Chemistry Borenium Cations for the Direct Electrophilic Borylation of Arenes A thesis submitted to The University of Manchester for the degree of Doctor of Philosophy in the Faculty of Engineering and Physical Sciences 2012 Alessandro Del Grosso School of Chemistry CONTENTS List of Schemes ....................................................................................................... 5 List of Tables ........................................................................................................... 7 List of Figures.......................................................................................................... 8 Abstract ................................................................................................................. 10 List of abbreviations .............................................................................................. 13 Chapter 1. Introduction ......................................................................................... 15 1.1 Background ................................................................................................. 15 1.2 Preparation of aromatic boronic acids and esters ......................................... 15 1.2.1 Transmetallation pathway .................................................................... 15 1.2.2 Metal catalysed pathway ...................................................................... 17 1.2.3 Cycloaddition pathway ........................................................................ 23 1.2.4 Electrophilic aromatic substitution pathway ......................................... 25 1.3 Boron monocations ..................................................................................... 33 1.3.1 Borinium and boronium cations ........................................................... 33 1.3.2 Borenium cations ................................................................................. 36 1.3.2.1 Preparation of borenium cations by halide abstraction .................. 36 1.3.2.2 Preparation of borenium cations by hydride abstraction ............... 41 1.3.2.3 Preparation of borenium cations by nucleophilic displacement ..... 43 1.3.2.4 Preparation of borenium cations by electrophilic attack ................ 44 1.4 Borenium cations in organic synthesis ......................................................... 46 1.5 Summary and scope of thesis....................................................................... 50 References ........................................................................................................ 52 Chapter 2. Catalytic (in Brønsted super-acid) arene borylation ............................. 62 2.1 Introduction................................................................................................. 62 2 2.2 Lewis acidity ............................................................................................... 63 2.2.1 Assessment of the Lewis Acidity by the Gutmann-Beckett method ...... 64 2.2.2 Assessment of the Lewis Acidity by the Child method ......................... 66 2.3 Arene Borylation ......................................................................................... 70 2.3.1 Stoichiometric Arene Borylation ......................................................... 70 2.3.2 Catalytic Arene Borylation .................................................................. 72 2.4 Use of other Anions .................................................................................... 81 2.5 Use of other boranes .................................................................................... 82 2.6 Mechanistic consideration ........................................................................... 87 2.7 Conclusions................................................................................................. 91 Experimental section ......................................................................................... 93 Crystallographic Details .................................................................................. 107 References ...................................................................................................... 109 Chapter 3. Arene borylation with catecholborenium cations ............................... 113 3.1 Introduction............................................................................................... 113 3.2 Synthesis of catecholborenium cations ...................................................... 113 3.3 Direct C-H Arene Borylation by borenium cation ...................................... 125 3.4 Studies on catecholboryl migration ............................................................ 131 3.5 Direct C-H Arene borylation with [CatB(NEt3)][GaCl4] and [CatB(NEt3)][FeCl4] ................................................................................. 135 3.6 Transesterification reaction ....................................................................... 136 3.7 Direct C-H arene borylation with [Cl4CatB(NEt3)][AlCl4] ......................... 140 3.8 Effect of the Lewis base in the arene borylation......................................... 141 3.9 Arene borylation with [CatB(NEt3)][closo-CB11H6Br6] ............................. 144 3.10 Borylation without borenium cation ........................................................ 148 3 3.11 Kinetic studies ......................................................................................... 153 3.12 Conclusions ............................................................................................. 155 Experimental section ....................................................................................... 157 Crystallographic Details .................................................................................. 193 References ...................................................................................................... 200 Chapter 4. Arene borylation with dichloroborenium cations ............................... 205 4.1 Introduction............................................................................................... 205 4.2 Synthesis and characterization of dihaloborenium cations ......................... 206 4.3 Arene borylation ....................................................................................... 218 4.4 Conclusions............................................................................................... 224 Experimental section ....................................................................................... 226 Crystallographic Details .................................................................................. 241 References ...................................................................................................... 245 4 LIST OF SCHEMES Scheme 1.1 ............................................................................................................ 19 Scheme 1.2 ............................................................................................................ 27 Scheme 1.3 ............................................................................................................ 29 Scheme 1.4 ............................................................................................................ 30 Scheme 1.5 ............................................................................................................ 31 Scheme 1.6 ............................................................................................................ 32 Scheme 1.7 ............................................................................................................ 32 Scheme 1.8 ............................................................................................................ 35 Scheme 1.9 ............................................................................................................ 36 Scheme 1.10 .......................................................................................................... 42 Scheme 1.11 .......................................................................................................... 44 Scheme 1.12 .......................................................................................................... 47 Scheme 1.13 .......................................................................................................... 48 Scheme 1.14 .......................................................................................................... 49 Scheme 1.15 .......................................................................................................... 49 Scheme 1.16 .......................................................................................................... 51 Scheme 2.1 ............................................................................................................ 67 Scheme 2.2 ............................................................................................................ 68 Scheme 2.3 ............................................................................................................ 73 Scheme 2.4 ............................................................................................................ 78 Scheme 2.5 ............................................................................................................ 78 Scheme 2.6 ............................................................................................................ 80 Scheme 2.7 ...........................................................................................................
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