Synthesis and Modifications of Porphyrinoids (Topics in Heterocyclic Chemistry Book 33)

The McMurry Reaction in Porphyrinoid Chemistry, by Kevin M. Smith Meso-tetraarylporphyrins: synthetic strategies and reactivity profiles based on nitro/amino substituents, by Maria da Graça Neves Functionalization of corroles, by José Cavaleiro Degradation pathways for porphyrinoids, by Jacek Wojaczynski Synthetic routes to porphyrinoids, by Sara Nardis Recent developments of non covalent porphyrin assemblies, by Donato Monti Preface 6 Contents 8 The McMurry Reaction in Porphyrinoid Chemistry 9 1 The McMurry Reaction 10 2 Macrocyclization Reactions 10 2.1 Porphycenes 10 2.2 Other Porphyrin Isomers 12 2.3 Dideazaporphyrin System 13 2.4 Stretched Porphycenes 13 2.5 Meso-Meso Linked Bisporphyrin 16 3 McMurry Reactions Around the Periphery of Tetrapyrrole Macrocycles 16 3.1 1,2-Diporphyrinylethenes 16 3.1.1 From beta-Formylporphyrins 16 3.1.2 From Meso-Formyl- and Meso-Formylvinylporphyrins 17 3.2 1,2-Bis(Chlorinyl)Ethenes 30 3.2.1 From beta-Formylchlorins 30 3.2.2 From Meso-Formylchlorins 31 3.2.3 From beta-Ketochlorins 35 4 Conclusion 37 References 40 Meso-Tetraarylporphyrins Bearing Nitro or Amino Groups: Synthetic Strategies and Reactivity Profiles 43 1 Introduction 44 2 Synthesis and Reactivity of Nitroporphyrins 44 2.1 Synthesis of Meso-(Nitrophenyl)porphyrins 44 2.2 Synthesis of beta-Nitro-Meso-Tetraarylporphyrins 47 3 Functionalization of Porphyrins via Nitro Groups 51 3.1 Functionalization of Meso-(Nitrophenyl)porphyrins 51 3.2 Functionalization of beta-Nitroporphyrins 53 4 Synthesis of Aminoporphyrins 59 5 Functionalization of Aminoporphyrins 60 5.1 Via Amide Bonds 60 5.2 Via Alkylation of the Amino Group 64 5.3 Via Transition Metal Catalysis 65 5.4 Via Diazonium Salts 67 5.5 The Dual Behavior of Aminoporphyrins 71 5.6 beta-Iminoporphyrins as Heterodienes 72 5.7 Aminoporphyrins as Carbene Acceptors 74 5.8 Aminoporphyrins in the Construction of New Assemblies 76 6 Conclusions 79 References 79 Functionalization of Corroles 87 1 Introduction 88 1.1 Corrole Inner Core Reactions 90 2 Key Substituents for Further Functionalization of Corroles 94 2.1 Halo Group 94 2.2 Chlorosulfonic Group 98 2.3 Formyl Group 100 2.4 Carboxylic Group 102 2.5 Vinyl Group 103 2.6 Nitro Group 105 2.7 Amino Group 112 3 Nucleophilic Substitutions 116 4 Cycloaddition Reactions 120 5 Functionalization of Corroles Mediated by Transition Metal Complexes 128 6 Final Remarks 143 References 143 Degradation Pathways for Porphyrinoids 150 1 Scope and Limitations 151 2 Degradation Used as Analytical Tool 153 3 Ring Opening by Oxidants 153 3.1 Oxidation of Porphyrins and Their Complexes 154 3.2 Degradation of Metalloporphyrin Catalysts 163 3.3 Oxidation of N-Confused Porphyrins 164 3.4 Oxidation of Corroles 166 4 Photooxidation of Tetrapyrroles 167 4.1 Photooxidation of Porphyrins, N-Confused Porphyrins and Phlorins 168 4.2 Photooxidation of Corroles 173 5 Coupled Oxidation 177 5.1 Oxophlorins 177 5.2 Verdohemes 180 5.3 Biliverdins 183 5.4 Regioselectivity of Coupled Oxidation 187 6 Biodegradation of Tetrapyrrolic Macrocycles 188 6.1 Heme Oxygenase 189 6.2 Chlorophyll Degradation 192 7 Summary: Future Directions 194 References 194 Synthetic Routes to Unsymmetrical Porphyrins 210 1 Introduction 211 2 Synthetic Routes to Unsymmetrical Porphyrins 212 2.1 Statistical Approach 212 2.2 [2+2] Routes 215 2.3 [3+1] Route 216 2.4 Via Bilanes 218 3 Functionalization of the Macrocycle 218 4 Other Methods 222 5 Applications 224 6 Conclusion 231 References 231 Recent Advancements in Chiral Porphyrin Self-Assembly 237 1 Introduction 238 2 The Origin of Chirality 238 3 Formation of Chiral Porphyrin Assemblies 243 3.1 Interaction of Porphyrin Derivatives with Chiral Surfactants 243 3.2 Supramolecular Chirality Driven by Covalently Linked Chiral Substituents 254 3.3 Spontaneous Symmetry Breaking at Air-Liquid Interfaces 272 3.4 Spontaneous Symmetry Breaking by Vortex Stirring 277 3.5 Templated Self-Assembly 282 3.6 Asymmetric Induction by Chiral Media 288 4 Conclusion 290 References 290 Index 298 Front Matter....Pages i-vii The McMurry Reaction in Porphyrinoid Chemistry....Pages 1-34 Meso -Tetraarylporphyrins Bearing Nitro or Amino Groups: Synthetic Strategies and Reactivity Profiles....Pages 35-78 Functionalization of Corroles....Pages 79-141 Degradation Pathways for Porphyrinoids....Pages 143-202 Synthetic Routes to Unsymmetrical Porphyrins....Pages 203-229 Recent Advancements in Chiral Porphyrin Self-Assembly....Pages 231-291 Back Matter....Pages 293-296 Kevin M. Smith The McMurry Reaction in Porphyrinoid Chemistry Maria da Graça Neves Meso-tetraarylporphyrins: synthetic strategies and reactivity profiles based on nitro/amino substituents José Cavaleiro Functionalization of corroles Jacek Wojaczynski Degradation pathways for porphyrinoids Sara Nardis Synthetic routes to porphyrinoids Donato Monti Recent developments of non covalent porphyrin assemblies