Microwave assisted organic synthesis

Front Matter......Page 1
Contributors......Page 3
Preface......Page 5
Table of Contents......Page 0
Table of Contents......Page 6
1.1 Introduction......Page 11
1.1.1 Microwave Radiation - Frequencies Available for Dielectric Heating......Page 12
1.2.1 Relaxation Times of Solvents......Page 14
1.2.2 Loss Tangents......Page 17
1.3 Dielectric Properties of Solids......Page 24
1.4 Comparison of Microwave and Conventional Heating......Page 28
1.6 References......Page 31
2.1 Introduction......Page 33
2.2 Stille Couplings......Page 34
2.3 Suzuki Couplings......Page 35
2.5 Heck Couplings......Page 39
2.6 Cyanation and Sonogashira Reactions......Page 41
2.7 Carbon-Heteroatom Coupling Reactions......Page 42
2.8 Asymmetric Molybdenum-Catalysed Allylic Alkylations......Page 44
2.9 Carbonylative Couplings......Page 45
2.9.1 Molybdenum Hexacarbonyl as a Solid CO-Releasing Reagent......Page 46
2.9.2 Formamides as Liquid CO-Releasing Reagents......Page 48
2.10 Outlook......Page 49
2.12 References......Page 51
3.1 Introduction......Page 54
3.2.1 Furans and Benzofurans......Page 55
3.2.2 Pyrroles, Indoles and Indolizines......Page 56
3.2.3 Thiophenes......Page 57
3.3.1 Imidazoles, Pyrazoles and Benzimidazoles......Page 58
3.3.2 Oxazoles, Isoxazoles, Thiazoles, Benzoxazoles and Benzothiazoles......Page 61
3.4.1 Triazoles......Page 63
3.4.2 Oxadiazoles......Page 64
3.4.3 Tetrazoles......Page 66
3.5.1 Pyridines, Quinolines, Isoquinolines and Fused Ring Analogues......Page 67
3.5.2 Benzopyrans......Page 69
3.6.1 Pyrimidines and Quinazolines......Page 71
3.7 Seven-Membered Heterocycles Containing at Least Two Heteroatoms:1,4 and 1,5-Benzodiazepines......Page 73
3.8.1 Fused Ring Heterocycles......Page 75
3.8.2 Fused Heterocycles Sharing at Least One Heteroatom......Page 78
3.9 Conclusion......Page 80
3.10 References......Page 81
4.1 Introduction......Page 85
4.2.1 C-C Multiple Bond Reduction Using Transfer Hydrogenation......Page 86
4.2.2 C-C Multiple Bond Reduction Using other Methods......Page 89
4.3 Reduction of Carbonyl Groups......Page 90
4.3.1 Carbonyl Reduction Using Borohydrides......Page 91
4.3.2 Carbonyl Reduction Under Meerwein-Ponndorf-Verley Conditions......Page 92
4.3.3 Carbonyl Reduction by Transfer Hydrogenation......Page 93
4.3.4 Carbonyl Reduction by the Cannizzaro Reaction......Page 94
4.3.5 Carbonyl Reduction Using other Methods......Page 96
4.4.1 Reduction of Imines......Page 97
4.4.2 Reduction of Nitro Groups......Page 100
4.4.3 Reduction of Hydrazones and Hydrazides......Page 103
4.5 Hydrodehalogenation......Page 105
4.7 References......Page 108
5.1.2 Designing the Method......Page 112
5.1.4 Multi-Component Versus One-Pot Synthesis......Page 113
5.2.1 Hantzsch Reaction......Page 115
5.2.3 Ugi Reaction......Page 117
5.2.4 Kindler Reaction......Page 119
5.2.5 Gewald Synthesis of 2-Acyl Amino Thiophenes......Page 120
5.2.7 Boronic Mannich Reaction......Page 121
5.2.9 Wittig Reaction......Page 122
5.3.1 (Triphenylphosphoranylidene)Ethenone......Page 124
5.3.2 N,N-Dimethylformamide Diethyl Acetal......Page 125
5.3.3 N,N-Dimethylformamide Diethyl Acetal on Solid Support......Page 126
5.4.1 Imidazoles......Page 127
5.4.2 Substituted Imidazoles......Page 128
5.4.3 Imidazo-Pyridines......Page 129
5.4.4 1,2,4-Triazine......Page 130
5.4.5 Indolizines......Page 131
5.4.7 Quinolines......Page 132
5.4.8 Quinazolin-4(3H)-Ones......Page 133
5.4.9 Substituted Pyrroles......Page 134
5.4.11 Spiroindoles......Page 135
5.4.12 a-Amino Phosphonates......Page 136
5.4.14 Multi-Component Reactions Using Isatoic Anhydride......Page 137
5.4.15 Pyrido[2,3-d]Pyrimidines......Page 138
5.6 References......Page 139
6.1 Introduction......Page 143
6.2.1 Heating a Heterogeneous Sample: Polymer Considerations......Page 144
6.2.2 Heating a Polymer-Solvent: A Binary Phase System......Page 145
6.2.3 Migration of the Reacting Species......Page 148
6.2.4 Reaction Heating: Solvent Considerations......Page 149
6.3 Microwave Reactions with Polymer-Supported Reagents......Page 151
6.3.2 Reductive Aminations......Page 152
6.3.4 Alkylation Reactions......Page 153
6.3.5 O-Alkylations of Carboxylic Acids......Page 154
6.3.6 Wittig Reactions......Page 156
6.3.7 Acylation Reactions......Page 157
6.3.8 Preparation of Isocyanides......Page 159
6.3.9 Synthesis of Thioamides......Page 160
6.3.10 Esterification of Alcohols Using Heterogeneous Acid Catalyst......Page 162
6.3.12 Beckmann Rearrangement......Page 163
6.3.13 Hydrogenation of Electron-Deficient Alkenes......Page 165
6.3.14 Heck Reactions......Page 166
6.3.16 Synthesis of 1,3,4-Oxadiazoles Using Polymer-Supported Burgess Reagent......Page 167
6.3.17 Preparation of a Substituted 2-Amino-1,3,4-Oxadiazole Library......Page 169
6.3.18 Synthesis of Thiohydantoins......Page 170
6.3.20 Microwave-Promoted Enzymatic Reactions......Page 171
6.3.22 The Synthesis of (+)-Plicamine......Page 174
6.3.23 Microwave-Assisted Scavenging Reactions......Page 177
6.4 Conclusion......Page 179
6.5 References......Page 180
7.1 Combinatorial Chemistry and Solid-Phase Organic Synthesis......Page 187
7.2 Microwave Chemistry and Solid-Phase Organic Synthesis......Page 188
7.2.2 Solvents......Page 189
7.2.3 Thermal and Mechanical Stability of Polymer Supports......Page 190
7.2.4 Equipment......Page 193
7.3.1 Peptide Synthesis and Related Examples......Page 194
7.3.2 Resin Functionalisation......Page 198
7.3.3 Transition-Metal Catalysis......Page 203
7.3.4 Substitution Reactions......Page 206
7.3.5 Multi-Component Chemistry......Page 211
7.3.6 Condensation Reactions......Page 214
7.3.7 Rearrangements......Page 216
7.3.8 Cleavage Reactions......Page 218
7.3.9 Miscellaneous......Page 222
7.3.10 Case Study: Pyrazinone Diels-Alder Chemistry......Page 226
7.4 Other Types of Supports......Page 228
7.6 References......Page 229
8.2 Timesavings Associated with Microwave-Assisted Synthesis......Page 232
8.3 Acceleration of Combinatorial Library Design and Development Stages......Page 234
8.3.1 The Contest......Page 236
8.3.2 The Thermal Approach......Page 237
8.3.3 The Microwave Approach......Page 239
8.4 New Advances in Microwave Technology......Page 240
8.5 References......Page 245
9.1 Introduction......Page 247
9.2 Mechanisms and Effects of Microwave Heating......Page 249
9.3 Approaches to Microwave-Assisted Organic Chemistry......Page 252
9.3.1 Solvent-Free Methods......Page 253
9.3.2 Scale-Up of Solvent-Free Methods......Page 254
9.3.3 Advantages and Disadvantages of Solvent-Free Methods......Page 257
9.3.4 Methods Employing Solvents......Page 258
9.3.5 Scale-Up of Methods Employing Solvents......Page 261
9.3.6 Advantages and Disadvantages of Methods Utilising Solvents......Page 269
9.4 Safety......Page 272
9.5 Tandem Technologies Involving Microwaves......Page 273
9.6 Concluding Remarks......Page 275
9.7 References......Page 276
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