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Carbon-Carbon Coupling Reactions Catalyzed by Heterogeneous PalladiumCatalysts


1. Introduction 133
1.1. Catalysts 135
1.2. Mechanistic Aspects 136
2. Suzuki Reactions 137
2.1. Pd on Carbon (Pd/C) 137
2.1.1. In the Presence of Phosphine Ligands 137
2.1.2. In the Absence of Phosphine Ligands 138
2.1.3. Ligand-Free Suzuki Coupling in Aqueous Surfactants140
2.1.4. Ligand-Free Suzuki Coupling underMicrowave or Ultrasound Conditions
140
2.2. Palladium on Metal Oxides 141
2.2.1. Palladium-Doped KF/Al2O3 141
2.2.2. Iron Oxide Nanoparticle-Supported Pd-N-Heterocyclic Carbene complexes
142
2.2.3. Palladium-Containing Perovskites 143
2.2.4. Miscellaneous Metal Oxides 143
2.3. Pd on Porous Aluminosilicates 143
2.4. Pd on Modified Silica 144
2.5. Pd on Clays and Other Inorganic Materials 145
3. Heck Reactions 146
3.1. Pd on Carbon (Pd/C) 146
3.2. Pd on Metal Oxides 149
3.3. Pd on Microporous and Mesoporous Supports 150
3.4. Pd on Modified Silica (Organic-InorganicHybrid Support) 151
3.5. Pd on Clay and Other Inorganic Materials 153
4. Sonogashira Reactions 154
4.1. Pd on Carbon (Pd/C) 154
4.1.1. In Anhydrous Media 154
4.1.2. In Organic Solvent/Water Mixtures 155
4.1.3. Copper-Free and Ligand-Free Sonogashira Coupling 157
4.2. Pd on Metal Oxides 158
4.3. Pd on Microporous and Mesoporous Supports 158
4.4. Pd on Modified Silica 159
4.5. Pd on Clay and Other Inorganic Materials 159
5. Stille, Fukuyama, and Negishi Reactions 159
5.1. Stille Reactions 159
5.1.1. Pd on Carbon (Pd/C) 159
5.1.2. Palladium on KF/Al2O3 159
5.1.3. Pd on Modified Silica (SiO2/TEG/Pd) 159
5.2. Fukuyama Reactions 159
5.2.1. Pd on Carbon (Pd/C) 159
5.2.2. Pd(OH)2 on Carbon (Perlman¡¯s Catalyst) 160
5.3. Pd/C-Catalyzed Negishi Reactions 160
6. Ullmann-Type Coupling Reactions 161
6.1. Pd/C-Catalyzed Aryl-Aryl Coupling 161
6.2. Pd/C-Catalyzed Homocoupling of Vinyl Halides 162
6.3. Pd/C-Catalyzed Intramolecular Coupling of Aryl and Vinyl Halides 162
7. Homocoupling of Arylboronic Acids, Pyridines,and Alkynes 162
7.1. Pd/C-Catalyzed Homocoupling of Arylboronic Acids (Suzuki-Type Homocoupling)162
7.2. Pd/C-Catalyzed Homocoupling of Pyridines 162
7.3. Pd/C-Catalyzed Homocoupling of Alkynes (Glaser-Type Coupling)164
8. Other Coupling Reactions 164
8.1. Cyanation of Aryl Bromides 164
8.2. Carbonylations 164
8.3. R-Arylations of Diethyl Malonate 165
8.4. Arylations of Aromatic Compounds 165
8.5. Allylations 166
8.6. Intermolecular Heck-Type Coupling 166
9. Pd on Solid Support in Tandem Reactions 167
9.1. Sonogashira Coupling in Tandem Reactions 167
9.2. Heck Coupling in Tandem Reactions 168
10. Conclusions and Perspectives 169
11. Abbreviations 170
12. Acknowledgments 170
13. References 170

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