Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 45b (eBook)

Science of Synthesis – Volume 45b: Aromatic Ring Assemblies, Polycyclic Aromatic Hydrocarbons, and Conjugated Polyenes 1
Title page 3
Imprint 5
Preface 6
Overview 8
Table of Contents 10
45.13 Product Class 13: Biaryls 40
45.13.1 Synthesis of Product Class 13 40
45.13.1.1 Synthesis Using Copper Catalysis 40
45.13.1.1.1 Method 1: The Ullmann Reaction 40
45.13.1.1.2 Method 2: Cross-Coupling Reactions 42
45.13.1.1.2.1 Variation 1: Using Boronic Acids 42
45.13.1.1.2.2 Variation 2: Using Organotin Reagents 43
45.13.1.2 The Suzuki Cross-Coupling Reaction 44
45.13.1.2.1 Method 1: Aryl Iodides in Suzuki Cross-Coupling Reactions 45
45.13.1.2.2 Method 2: Aryl Bromides in Suzuki Cross-Coupling Reactions 48
45.13.1.2.3 Method 3: Aryl Chlorides in Suzuki Cross-Coupling Reactions 55
45.13.1.2.4 Method 4: Aryl 4-Toluenesulfonates and Trifluoromethanesulfonates in Suzuki Cross-Coupling Reactions 60
45.13.1.2.5 Method 5: Diazonium Salts in Suzuki Cross-Coupling Reactions 64
45.13.1.2.6 Method 6: Synthesis of Hindered Biaryls Using the Suzuki Cross-Coupling Reaction 65
45.13.1.2.7 Method 7: Synthesis of Oligoaromatics Using the Suzuki Cross-Coupling Reaction 68
45.13.1.3 The Stille Cross-Coupling Reaction 70
45.13.1.3.1 Method 1: Aryl Iodides in Stille Cross-Coupling Reactions 71
45.13.1.3.2 Method 2: Aryl Bromides in Stille Cross-Coupling Reactions 72
45.13.1.3.3 Method 3: Aryl Chlorides in Stille Cross-Coupling Reactions 73
45.13.1.3.4 Method 4: Aryl Trifluoromethanesulfonates in Stille Cross-Coupling Reactions 74
45.13.1.3.5 Method 5: Synthesis of Hindered Biaryls Using the Stille Cross-Coupling Reaction 75
45.13.1.4 The Negishi Cross-Coupling Reaction 77
45.13.1.4.1 Method 1: Aryl Iodides in Negishi Cross-Coupling Reactions 77
45.13.1.4.2 Method 2: Aryl Bromides in Negishi Cross-Coupling Reactions 79
45.13.1.4.3 Method 3: Aryl Chlorides in Negishi Cross-Coupling Reactions 80
45.13.1.4.4 Method 4: Aryl Trifluoromethanesulfonates in Negishi Cross-Coupling Reactions 81
45.13.1.4.5 Method 5: Synthesis of Hindered Biaryls Using the Negishi Cross-Coupling Reaction 82
45.13.1.5 The Hiyama Cross-Coupling Reaction 84
45.13.1.5.1 Method 1: Aryl Iodides in Hiyama Cross-Coupling Reactions 84
45.13.1.5.2 Method 2: Aryl Bromides in Hiyama Cross-Coupling Reactions 87
45.13.1.5.3 Method 3: Aryl Chlorides in Hiyama Cross-Coupling Reactions 89
45.13.1.5.4 Method 4: Aryl Trifluoromethanesulfonates in Hiyama Cross-Coupling Reactions 91
45.13.1.5.5 Method 5: Synthesis of Oligoaromatics Using the Hiyama Cross-Coupling Reaction 92
45.13.1.6 The Kumada--Corriu Cross-Coupling Reaction 92
45.13.1.6.1 Method 1: Aryl Iodides in Kumada--Corriu Cross-Coupling Reactions 92
45.13.1.6.2 Method 2: Aryl Bromides in Kumada--Corriu Cross-Coupling Reactions 94
45.13.1.6.3 Method 3: Aryl Chlorides in Kumada--Corriu Cross-Coupling Reactions 95
45.13.1.6.4 Method 4: Aryl Trifluoromethanesulfonates and Arenesulfonates in Kumada--Corriu Cross-Coupling Reactions 96
45.13.1.6.5 Method 5: Synthesis of Hindered Biaryls Using the Kumada--Corriu Cross-Coupling Reaction 98
45.13.1.6.6 Method 6: Synthesis of Oligoaromatics Using the Kumada--Corriu Coupling Reaction 98
45.13.1.7 Direct Arylation 99
45.13.1.7.1 Method 1: Intramolecular Direct Arylation 99
45.13.1.7.2 Method 2: Intermolecular Direct Arylation 105
45.13.1.7.2.1 Variation 1: In the Presence of Directing Groups 105
45.13.1.7.2.2 Variation 2: Without Directing Groups 110
45.13.1.7.3 Method 3: Palladium-Catalyzed Domino/Cascade Reactions Involving Direct Arylation 111
45.14 Product Class 14: Arylalkanes 120
45.14.1 Synthesis of Product Class 14 120
45.14.1.1 Method 1: Friedel--Crafts Alkylation 120
45.14.1.1.1 Variation 1: Using Alkyl Halides 120
45.14.1.1.2 Variation 2: Using Alkenes 122
45.14.1.1.3 Variation 3: Using Alcohols 125
45.14.1.1.4 Variation 4: Using Esters 126
45.14.1.1.5 Variation 5: Asymmetric Friedel--Crafts Alkylation 127
45.14.1.2 Method 2: Alkylation of Aromatic Ketones with Alkenes by C--H Activation 129
45.14.1.3 Method 3: Alkylation via Transition-Metal-Catalyzed Cross-Coupling Reactions with Alkyl Electrophiles 129
45.14.1.3.1 Variation 1: Kumada Cross-Coupling Reaction 129
45.14.1.3.2 Variation 2: Suzuki Cross-Coupling Reaction 131
45.14.1.3.3 Variation 3: Negishi Cross-Coupling Reaction 132
45.14.1.3.4 Variation 4: Stille Cross-Coupling Reaction 134
45.14.1.3.5 Variation 5: Hiyama Cross-Coupling Reaction 134
45.14.1.4 Method 4: Alkylation via Transition-Metal-Catalyzed Cross-Coupling Reactions with Alkyl Nucleophiles 136
45.14.1.4.1 Variation 1: Kumada Cross-Coupling Reaction 136
45.14.1.4.2 Variation 2: Suzuki Cross-Coupling Reaction 137
45.14.1.4.3 Variation 3: Negishi Cross-Coupling Reaction 140
45.14.1.4.4 Variation 4: Hiyama Cross-Coupling Reaction 142
45.15 Product Class 15: Poly(phenylenes) 146
45.15.1 Product Subclass 1: Linear Poly(phenylenes) 146
45.15.1.1 Synthesis of Product Subclass 1 147
45.15.1.1.1 Method 1: Kovacic Procedure 147
45.15.1.1.2 Method 2: Dehalogenative Polycondensation Reactions of Disubstituted Benzenes Using Nickel(0) Complexes 148
45.15.1.1.2.1 Variation 1: Using Bis(.4-cycloocta-1,5-diene)nickel(0) 149
45.15.1.1.2.2 Variation 2: Using a Nickel Complex as the Catalyst and Zinc as the Reducing Reagent 151
45.15.1.1.3 Method 3: Grignard Coupling Reactions 152
45.15.1.1.4 Method 4: Suzuki Coupling Reactions 154
45.15.1.1.4.1 Variation 1: AB-Type Approach 154
45.15.1.1.4.2 Variation 2: AA/BB-Type Approach 156
45.15.1.1.5 Method 5: Stille Coupling Reactions 157
45.15.1.1.6 Method 6: Reactions Utilizing Intermediate Polymers 159
45.15.1.1.6.1 Variation 1: Aromatization by Decarboxylation of Soluble Precursor Polymers 159
45.15.1.1.6.2 Variation 2: Decarboxylation of a Precursor with a Poly(p-phenylene) Backbone 161
45.15.1.1.7 Method 7: Diels--Alder Polycondensations 161
45.15.2 Product Subclass 2: Macrocyclic Poly(phenylenes) 163
45.15.2.1 Synthesis of Product Subclass 2 163
45.15.2.1.1 Method 1: Reductive Coupling Reactions 163
45.15.2.1.2 Method 2: Suzuki Coupling Reactions 164
45.15.3 Product Subclass 3: Dendritic Poly(phenylenes) 165
45.15.3.1 Synthesis of Product Subclass 3 165
45.15.3.1.1 Method 1: Suzuki Coupling Reactions 165
45.15.3.1.2 Method 2: Diels--Alder Cycloaddition Reactions 166
45.16 Product Class 16: Poly(p-phenylenevinylenes) 170
45.16.1 Product Subclass 1: Unsubstituted Poly(p-phenylenevinylenes) 170
45.16.1.1 Synthesis of Product Subclass 1 170
45.16.1.1.1 Method 1: Polymerization of Sulfonium Salts 171
45.16.1.1.2 Method 2: Polymerization of Dithiocarbonates 172
45.16.1.1.3 Method 3: Polymerization of Dithiocarbamates 172
45.16.1.1.4 Method 4: Polymerization of Sulfinyl Compounds 173
45.16.1.1.5 Method 5: Ring-Opening Metathesis Polymerization 174
45.16.2 Product Subclass 2: Substituted, Soluble Poly(p-phenylenevinylenes) 175
45.16.2.1 Synthesis of Product Subclass 2 175
45.16.2.1.1 Method 1: Polymerization of Sulfonium Salts 176
45.16.2.1.2 Method 2: The Gilch Method 176
45.16.2.1.3 Method 3: Polymerization of Dithiocarbamates 178
45.16.2.1.4 Method 4: Wittig Reactions 179
45.16.2.1.5 Method 5: Horner Reactions 180
45.16.2.1.6 Method 6: Heck Coupling 181
45.16.2.1.7 Method 7: Stille Coupling 182
45.16.2.1.8 Method 8: Acyclic Diene Metathesis Polymerization 182
45.16.2.1.9 Method 9: Ring-Opening Metathesis Polymerization 183
45.16.2.1.10 Method 10: Polymerization of (Dichloromethyl)aryls 184
45.16.2.1.11 Method 11: McMurry Reaction 185
45.16.2.1.12 Method 12: Knoevenagel Condensation 185
45.17 Product Class 17: Poly(xylylenes) 190
45.17.1 Product Subclass 1: Poly(p-xylylenes) 191
45.17.1.1 Synthesis of Product Subclass 1 191
45.17.1.1.1 Method 1: Wurtz--Fittig Dehalogenation of 1,4-Bis(halomethyl)arenes in the Presence of a Metal 191
45.17.1.1.2 Method 2: Friedel--Crafts Coupling of Benzene with 1,2-Dihaloethanes, or of (2-Haloethyl)benzenes 191
45.17.1.1.3 Method 3: Synthesis by Isomerization Polymerization of Diazo Compounds 192
45.17.1.1.4 Method 4: Reductive Coupling of Aromatic Dialdehydes 192
45.17.1.1.5 Method 5: Polyrecombination in the Presence of Peroxide 193
45.17.1.1.6 Method 6: Hofmann and Hofmann-Analogous Degradations 193
45.17.1.1.6.1 Variation 1: Of Trimethyl(4-methylbenzyl)ammonium Salts 193
45.17.1.1.6.2 Variation 2: Of Trimethyl[4-(trimethylsilylmethyl)benzyl]ammonium Halides 194
45.17.1.1.7 Method 7: Electrochemical Reduction of 1,4-Bis(halomethyl)benzenes 195
45.17.1.1.8 Method 8: Dehydrohalogenation with Base 197
45.17.1.1.8.1 Variation 1: Of 1-(Halomethyl)-4-methylarenes 197
45.17.1.1.8.2 Variation 2: Of 1,4-Bis(halomethyl)arenes 198
45.17.1.1.8.3 Variation 3: Of p-Xylylenebis(dialkylsulfonium) Dihalide Salts 200
45.17.1.1.8.4 Variation 4: Of 4-(Chloromethyl)benzyl Sulfoxides or Sulfones 201
45.17.1.1.9 Method 9: Chemical Vapor Deposition by Pyrolysis 202
45.17.1.1.9.1 Variation 1: Of p-Xylenes 202
45.17.1.1.9.2 Variation 2: Of Esters of 1,4-Phenylenedimethanols 203
45.17.1.1.9.3 Variation 3: Of 1-(Halomethyl)- or 1-(Dihalomethyl)-4-methylbenzenes, or 1,4-Bis(dihalomethyl)benzenes 204
45.17.1.1.9.4 Variation 4: Of Cyclophanes 205
45.17.1.1.9.5 Variation 5: Of a Spiro Compound 207
45.17.1.1.10 Method 10: Dehalogenation of 1,4-Bis(trihalomethyl)benzenes via Chemical Vapor Deposition by Pyrolysis with Metal Contact 207
45.17.2 Product Subclass 2: Poly(m-xylylenes) 208
45.17.2.1 Synthesis of Product Subclass 2 208
45.17.2.1.1 Method 1: Wurtz--Fittig Dehalogenation of 1,3-Bis(halomethyl)benzenes in the Presence of a Metal 208
45.17.2.1.2 Method 2: Reductive Coupling of Aromatic Dialdehydes 209
45.17.3 Product Subclass 3: Poly(o-xylylenes) 209
45.17.3.1 Synthesis of Product Subclass 3 209
45.17.3.1.1 Method 1: Wurtz--Fittig Dehalogenation of a 1,2-Bis(halomethyl)benzene in the Presence of a Metal 209
45.17.3.1.2 Method 2: Electrochemical Reduction of 1,2-Bis(halomethyl)benzenes 210
45.17.3.1.3 Method 3: Ring-Opening Reactions 210
45.17.3.1.3.1 Variation 1: Of Spiro Compounds 210
45.17.3.1.3.2 Variation 2: Of Benzocyclobutenes 211
45.18 Product Class 18: Polystyrenes 216
45.18.1 Product Subclass 1: Linear Polystyrenes 216
45.18.1.1 Synthesis of Product Subclass 1 216
45.18.1.1.1 Method 1: Conventional Radical Polymerization 217
45.18.1.1.1.1 Variation 1: Addition--Fragmentation Chain Transfer (AFCT) 218
45.18.1.1.2 Method 2: Controlled/Living Radical Polymerization (CLRP) 219
45.18.1.1.2.1 Variation 1: Nitroxide-Mediated Radical Polymerization (NMP) 220
45.18.1.1.2.2 Variation 2: Atom Transfer Radical Polymerization (ATRP) 221
45.18.1.1.2.3 Variation 3: Reversible Addition--Fragmentation Chain Transfer (RAFT) 222
45.18.1.1.2.4 Variation 4: Organotellurium-Mediated Living Radical Polymerization (TERP) 223
45.18.1.1.3 Method 3: Living Anionic Polymerization 223
45.18.1.1.4 Method 4: Living Cationic Polymerization 224
45.18.1.1.5 Method 5: Coordination Polymerization 225
45.18.1.1.5.1 Variation 1: Isotactic Polymerization 226
45.18.1.1.5.2 Variation 2: Syndiotactic Polymerization 226
45.18.1.1.6 Method 6: Modification of Substituents 227
45.18.1.1.6.1 Variation 1: Click Chemistry Approach 227
45.18.1.1.6.2 Variation 2: Miscellaneous Organic Functional Group Transformations 228
45.18.1.2 Applications of Product Subclass 1 in Organic Synthesis 229
45.18.1.2.1 Method 1: Soluble Polystyrene Supports Made by Controlled/Living Radical Polymerization 230
45.18.2 Product Subclass 2: Branched Polystyrenes 230
45.18.2.1 Synthesis of Product Subclass 2 230
45.18.2.1.1 Method 1: Alkoxyamine-Initiated Radical Polymerization 231
45.18.2.1.2 Method 2: Controlled/Living Radical Copolymerization with Macromonomers 232
45.18.3 Product Subclass 3: Cross-Linked Polystyrenes 232
45.18.3.1 Synthesis of Product Subclass 3 233
45.18.3.1.1 Method 1: Suspension Copolymerization of Styrene with Cross-Linking Monomers 233
45.19 Product Class 19: Naphthalenes, Anthracenes, 9H-Fluorenes, and Other Acenes 238
45.19.1 Product Subclass 1: Naphthalenes 239
45.19.1.1 Synthesis of Product Subclass 1 239
45.19.1.1.1 Synthesis by Ring-Closure Reactions 239
45.19.1.1.1.1 Method 1: Formation of Three C--C Bonds 240
45.19.1.1.1.1.1 Variation 1: Palladium-Catalyzed Cyclization of Alkynes and Alkenes 240
45.19.1.1.1.1.2 Variation 2: Palladium-Catalyzed Cyclization of Alkynes 240
45.19.1.1.1.1.3 Variation 3: Iridium-Catalyzed Cyclization 241
45.19.1.1.1.1.4 Variation 4: Copper-Catalyzed Cyclization of Organozirconium Compounds 241
45.19.1.1.1.1.5 Variation 5: Insertion of a Nickel--Benzyne Complex 242
45.19.1.1.1.2 Method 2: Formation of Two C--C Bonds with a C2 Unit 243
45.19.1.1.1.2.1 Variation 1: Titanium-Catalyzed Cyclization 243
45.19.1.1.1.2.2 Variation 2: Palladium-Catalyzed Cyclization of Organozirconium Compounds 243
45.19.1.1.1.2.3 Variation 3: Palladium-Catalyzed Cyclization of Vinyl and Aryl Iodides 244
45.19.1.1.1.2.4 Variation 4: Diels--Alder Reaction of o-Quinodimethanes 245
45.19.1.1.1.2.5 Variation 5: Diels--Alder Reaction of Organotungsten Compounds 246
45.19.1.1.1.2.6 Variation 6: Electrophilic Cyclization 246
45.19.1.1.1.2.7 Variation 7: Lewis Acid Catalyzed Cyclization 247
45.19.1.1.1.2.8 Variation 8: Cyclization of Phosphonium Salts with Enolates 248
45.19.1.1.1.3 Method 3: Formation of Two C--C Bonds with a C3 Unit 249
45.19.1.1.1.3.1 Variation 1: Cyclization with Enones 249
45.19.1.1.1.3.2 Variation 2: Cyclization with 3-Oxo Acetals 250
45.19.1.1.1.3.3 Variation 3: Cyclization with 3-Oxo Dithioacetals 250
45.19.1.1.1.3.4 Variation 4: Cyclization with Grignard Reagents 251
45.19.1.1.1.4 Method 4: Formation of Two C--C Bonds with a C4 Unit 252
45.19.1.1.1.4.1 Variation 1: Diels--Alder Reaction with Cyclopentadienones 253
45.19.1.1.1.4.2 Variation 2: Diels--Alder Reaction with Pyrroles 253
45.19.1.1.1.4.3 Variation 3: Diels--Alder Reaction with Furans 254
45.19.1.1.1.5 Method 5: Formation of One C--C Bond to a Benzene Ring 256
45.19.1.1.1.5.1 Variation 1: Friedel--Crafts Acylation 257
45.19.1.1.1.5.2 Variation 2: Friedel--Crafts Alkylation 257
45.19.1.1.1.5.3 Variation 3: Lewis Acid Catalyzed Rearrangement of Vinylidenecyclopropanes 258
45.19.1.1.1.5.4 Variation 4: Electrophilic Cyclization of Alkynes 259
45.19.1.1.1.5.5 Variation 5: Base-Catalyzed Cyclization of Enynes 259
45.19.1.1.1.5.6 Variation 6: Base-Catalyzed Rearrangement of Methylenetetrahydrofurans 260
45.19.1.1.1.6 Method 6: Formation of One C--C Bond at Other Sites 261
45.19.1.1.1.6.1 Variation 1: Bergman Cyclization 261
45.19.1.1.1.6.2 Variation 2: Tellurium-Mediated Cycloaddition 262
45.19.1.1.1.6.3 Variation 3: Reductive Cyclization 262
45.19.1.1.1.6.4 Variation 4: Ring-Closing Metathesis 263
45.19.1.1.1.6.5 Variation 5: Metal-Catalyzed Cyclization 263
45.19.1.1.2 Synthesis by Ring Transformation 264
45.19.1.1.2.1 Method 1: Valence Isomerism 264
45.19.1.1.2.1.1 Variation 1: From Dewar Benzenes 264
45.19.1.1.2.1.2 Variation 2: From Benzvalenes 265
45.19.1.1.2.2 Method 2: Rearrangement Reactions 265
45.19.1.1.2.2.1 Variation 1: Metal-Mediated Ring Expansion 265
45.19.1.1.2.2.2 Variation 2: Thermal Ring Expansion 266
45.19.1.1.2.2.3 Variation 3: Acid-Catalyzed Ring Contraction 266
45.19.1.1.3 Synthesis by Aromatization 267
45.19.1.1.3.1 Method 1: Oxidation of Hydrogenated Compounds 267
45.19.1.1.3.1.1 Variation 1: Dehydrogenation over Palladium on Carbon 267
45.19.1.1.3.1.2 Variation 2: Dehydrogenation by Sulfur 268
45.19.1.1.3.1.3 Variation 3: Dehydrogenation by Benzoquinones 269
45.19.1.1.3.1.4 Variation 4: Other Methods 269
45.19.1.1.3.2 Method 2: Synthesis from Tetralones or Naphthoquinones 270
45.19.1.1.3.2.1 Variation 1: Direct Conversion into Naphthalenes 270
45.19.1.1.3.2.2 Variation 2: Stepwise Conversion into Naphthalenes 271
45.19.1.1.3.3 Method 3: Elimination Reactions 272
45.19.1.1.3.3.1 Variation 1: Dehydration 272
45.19.1.1.3.3.2 Variation 2: Dehydrobromination 273
45.19.1.1.4 Synthesis by Substitution of Existing Substituents 273
45.19.1.1.4.1 Method 1: Substitution of Hydrogen 273
45.19.1.1.4.1.1 Variation 1: Friedel--Crafts Alkylation 273
45.19.1.1.4.2 Method 2: Substitution of Carbon 274
45.19.1.1.4.2.1 Variation 1: Dealkylation 274
45.19.1.1.4.3 Method 3: Substitution of Heteroatoms 275
45.19.1.1.4.3.1 Variation 1: Coupling with Organoboranes 275
45.19.1.1.4.3.2 Variation 2: Coupling with Grignard Reagents 276
45.19.1.1.4.3.3 Variation 3: Coupling with Organoaluminum Complexes 277
45.19.1.1.4.3.4 Variation 4: Coupling with Other Organometallic Reagents 278
45.19.1.1.5 Synthesis by Modification of Substituents 278
45.19.1.1.5.1 Method 1: Alkylation of Alkyl Substituents 278
45.19.1.1.5.2 Method 2: Dehalogenation of Halomethyl Groups 279
45.19.1.1.5.3 Method 3: Deoxygenation of Hydroxymethyl Groups 280
45.19.1.1.5.4 Method 4: Reduction of Acyl Groups 280
45.19.2 Product Subclass 2: Anthracenes 281
45.19.2.1 Synthesis of Product Subclass 2 281
45.19.2.1.1 Synthesis by Ring-Closure Reactions 281
45.19.2.1.1.1 Method 1: Formation of the Two Terminal Benzene Rings 281
45.19.2.1.1.1.1 Variation 1: Palladium-Catalyzed Cyclization 281
45.19.2.1.1.1.2 Variation 2: Copper-Catalyzed Cyclization with Organozirconium Compounds 282
45.19.2.1.1.1.3 Variation 3: Diels--Alder Reaction with Furans and Pyrroles 283
45.19.2.1.1.1.4 Variation 4: Diels--Alder Reaction of Benzo-1,4-quinone 284
45.19.2.1.1.1.5 Variation 5: Bergman Cyclization 285
45.19.2.1.1.2 Method 2: Formation of the Central Benzene Ring and a Terminal Benzene Ring 286
45.19.2.1.1.3 Method 3: Formation of the Central Benzene Ring 287
45.19.2.1.1.3.1 Variation 1: Acid-Catalyzed Cyclization of Benzyl Acetates 287
45.19.2.1.1.3.2 Variation 2: Thermal Cyclodehydration 287
45.19.2.1.1.3.3 Variation 3: Acid-Catalyzed Cyclization of Ketones 288
45.19.2.1.1.3.4 Variation 4: Acid-Catalyzed Cyclization of Azines 288
45.19.2.1.1.3.5 Variation 5: Diels--Alder Reaction of Isobenzofuran 289
45.19.2.1.1.3.6 Variation 6: Diels--Alder Reaction of Isoindoles 290
45.19.2.1.1.4 Method 4: Synthesis by Formation of a Terminal Benzene Ring 291
45.19.2.1.1.4.1 Variation 1: Iridium-Catalyzed Cyclization 291
45.19.2.1.1.4.2 Variation 2: Diels--Alder Reaction of Dienes 291
45.19.2.1.1.4.3 Variation 3: Bergman Cyclization 292
45.19.2.1.2 Synthesis by Ring Transformation 293
45.19.2.1.2.1 Method 1: Ring Contraction by Pyrolysis 293
45.19.2.1.3 Synthesis by Aromatization 294
45.19.2.1.3.1 Method 1: Oxidation of Dihydroanthracenes 294
45.19.2.1.3.1.1 Variation 1: Dehydrogenation by Conventional Methods 294
45.19.2.1.3.1.2 Variation 2: Dehydrogenation via an Anion 295
45.19.2.1.3.1.3 Variation 3: Dehydrogenation by Oxygen 296
45.19.2.1.3.2 Method 2: Synthesis from Oxygenated Compounds 297
45.19.2.1.3.2.1 Variation 1: Alkylation of Anthraquinones 297
45.19.2.1.3.2.2 Variation 2: Alkylation of Anthracen-9(10H)-ones 298
45.19.2.1.3.2.3 Variation 3: Reduction of Anthraquinones 299
45.19.2.1.3.2.4 Variation 4: Reduction of Anthracenones 300
45.19.2.1.3.3 Method 3: Elimination Reactions 301
45.19.2.1.3.3.1 Variation 1: Deoxygenation 301
45.19.2.1.3.3.2 Variation 2: Retro-Diels--Alder Reaction 302
45.19.2.1.4 Synthesis by Substitution of Existing Substituents 302
45.19.2.1.4.1 Method 1: Substitution of Hydrogen 302
45.19.2.1.4.1.1 Variation 1: Friedel--Crafts Alkylation 302
45.19.2.1.4.1.2 Variation 2: Alkylation of 9,10-Dihydroanthracenes 303
45.19.2.1.4.1.3 Variation 3: Alkylation of 1,4-Dihydroanthracene 305
45.19.2.1.4.2 Method 2: Substitution of Carbon 305
45.19.2.1.4.2.1 Variation 1: Dealkylation 305
45.19.2.1.4.3 Method 3: Substitution of Heteroatoms 306
45.19.2.1.4.3.1 Variation 1: Nucleophilic Alkylation 306
45.19.2.1.4.3.2 Variation 2: Alkylation via Organolithium Compounds 307
45.19.2.1.4.3.3 Variation 3: Cross-Coupling Reactions 308
45.19.2.1.5 Synthesis by Modification of Substituents 309
45.19.2.1.5.1 Method 1: Reduction of Acyl Groups 309
45.19.3 Product Subclass 3: 9H-Fluorenes 310
45.19.3.1 Synthesis of Product Subclass 3 310
45.19.3.1.1 Synthesis by Ring-Closure Reactions 311
45.19.3.1.1.1 Method 1: Formation of the Five-Membered Ring by Formation of Two Bonds 311
45.19.3.1.1.1.1 Variation 1: Palladium-Catalyzed Cyclizations 311
45.19.3.1.1.2 Method 2: Formation of the Five-Membered Ring by C9--CAr Bond Formation 312
45.19.3.1.1.2.1 Variation 1: Niobium-Catalyzed Cyclizations 312
45.19.3.1.1.2.2 Variation 2: Thermal Cyclization 312
45.19.3.1.1.2.3 Variation 3: Electrophilic Cyclization 313
45.19.3.1.1.3 Method 3: Formation of the Five-Membered Ring by CAr--CAr Bond Formation 313
45.19.3.1.1.3.1 Variation 1: Metal-Catalyzed Coupling 313
45.19.3.1.1.3.2 Variation 2: Palladium-Catalyzed Coupling 314
45.19.3.1.1.3.3 Variation 3: Electrophilic Substitution 314
45.19.3.1.1.4 Method 4: Formation of a Terminal Benzene Ring 315
45.19.3.1.1.4.1 Variation 1: Diels--Alder Reaction 315
45.19.3.1.1.4.2 Variation 2: Cyclization of Indene Derivatives 316
45.19.3.1.2 Synthesis by Reduction of Oxygenated Compounds 317
45.19.3.1.2.1 Method 1: Reduction of 9H-Fluoren-9-ones 317
45.19.3.1.2.2 Method 2: Reduction of 9H-Fluoren-9-ols 318
45.19.3.1.2.3 Method 3: Elimination and Reduction of 9H-Fluoren-9-ols 318
45.19.3.1.3 Synthesis by Substitution of Existing Substituents 319
45.19.3.1.3.1 Method 1: Substitution of Aromatic Hydrogen 319
45.19.3.1.3.1.1 Variation 1: Friedel--Crafts Alkylation 319
45.19.3.1.3.1.2 Variation 2: Transalkylation 320
45.19.3.1.3.2 Method 2: Substitution of Hydrogen at C9 321
45.19.3.1.3.2.1 Variation 1: Substitution Using Alkyl Halides 321
45.19.3.1.3.2.2 Variation 2: Substitution by Sodium Alkoxides 322
45.19.3.1.3.3 Method 3: Substitution of Carbon 323
45.19.3.1.3.3.1 Variation 1: Dealkylation 323
45.19.3.1.3.3.2 Variation 2: Decarboxylation 323
45.19.3.1.4 Synthesis by Modification of a Substituent 324
45.19.3.1.4.1 Method 1: Reduction of a Substituted Methyl Group 324
45.19.3.1.4.2 Method 2: Alkylation of an Acyl Group 324
45.19.3.1.4.3 Method 3: Reduction of an Acyl Group 325
45.19.4 Product Subclass 4: Higher Acenes 325
45.19.4.1 Synthesis of Product Subclass 4 325
45.19.4.1.1 Synthesis by Ring-Closure Reactions 326
45.19.4.1.1.1 Method 1: Metal-Catalyzed Cyclization 326
45.19.4.1.1.1.1 Variation 1: Cyclization of an Alkyne with Organozirconium Compounds 326
45.19.4.1.1.1.2 Variation 2: Cyclization of Iodoarenes with Organozirconium Compounds 327
45.19.4.1.1.2 Method 2: Condensation Reactions 329
45.19.4.1.1.2.1 Variation 1: Thermal Cyclodehydration 329
45.19.4.1.1.2.2 Variation 2: Friedel--Crafts Acylation 329
45.19.4.1.1.2.3 Variation 3: Condensation of Dialdehydes and Diketones 330
45.19.4.1.1.2.4 Variation 4: Condensation of Dialdehydes and Diesters 331
45.19.4.1.1.3 Method 3: Bergman Cyclization 332
45.19.4.1.1.4 Method 4: Diels--Alder Reaction 333
45.19.4.1.1.4.1 Variation 1: Reaction of Furans with Arynes 333
45.19.4.1.1.4.2 Variation 2: Reaction of Pyrroles with Arynes 335
45.19.4.1.1.4.3 Variation 3: Reaction of Bicyclic Pentaenes with Arynes 335
45.19.4.1.1.4.4 Variation 4: Reaction of o-Quinodimethanes with Dienophiles 336
45.19.4.1.1.4.5 Variation 5: Reaction of Dienes and 1,4-Quinones 338
45.19.4.1.2 Synthesis by Ring Transformation 339
45.20 Product Class 20: Cyclobutabenzenes, Biphenylenes, and [N]Phenylenes 348
45.20.1 Product Subclass 1: Cyclobutabenzenes 349
45.20.1.1 Synthesis of Product Subclass 1 349
45.20.1.1.1 Synthesis by Ring-Closure Reactions 349
45.20.1.1.1.1 Method 1: Thermal Reaction of Dienediynes 349
45.20.1.1.1.2 Method 2: Thermal Reaction of Dialk-1-ynylcyclobutenes 350
45.20.2 Product Subclass 2: Biphenylenes 351
45.20.2.1 Synthesis of Product Subclass 2 352
45.20.2.1.1 Synthesis by Ring-Closure Reactions 352
45.20.2.1.1.1 Method 1: Formation of Two Rings by Cobalt-Catalyzed Cyclization of Alkynes 352
45.20.2.1.1.2 Method 2: Formation of the Cyclobutadiene Ring by Dimerization of Benzynes 353
45.20.2.1.1.2.1 Variation 1: Generated from 2-Diazoniobenzoate 354
45.20.2.1.1.2.2 Variation 2: Generated by Elimination from 2-Metalated Halobenzenes 354
45.20.2.1.1.2.3 Variation 3: Generated by Oxidation of 1-Aminobenzotriazole 355
45.20.2.1.1.3 Method 3: Formation of the Four-Membered Ring by Coupling Reactions 356
45.20.2.1.1.3.1 Variation 1: Copper-Catalyzed Coupling of Organo Halides 356
45.20.2.1.1.3.2 Variation 2: Copper-Catalyzed Coupling of Organolithiums 357
45.20.2.1.1.3.3 Variation 3: Copper-Catalyzed Coupling of Organozincs 358
45.20.2.1.1.3.4 Variation 4: Coupling of Organomercurials 360
45.20.2.1.1.3.5 Variation 5: Thermal Radical Coupling 361
45.20.2.1.1.4 Method 4: Formation of One Benzene Ring by Cycloaddition of Cyclobutabenzene 361
45.20.2.1.1.4.1 Variation 1: With o-Quinodimethanes 361
45.20.2.1.1.4.2 Variation 2: With Other Dienes 362
45.20.2.1.2 Synthesis by Substitution 363
45.20.2.1.2.1 Method 1: Substitution of Hydrogen 363
45.20.2.1.2.1.1 Variation 1: Electrophilic Substitution 363
45.20.2.1.2.1.2 Variation 2: Substitution of Lithiated Biphenylene 364
45.20.2.1.2.2 Method 2: Substitution of Non-Hydrogen Atoms 365
45.20.2.1.2.2.1 Variation 1: Substitution of Silicon 365
45.20.2.1.2.2.2 Variation 2: Substitution of Halogen 365
45.20.2.1.3 Synthesis by Modification of Substituents 366
45.20.2.1.3.1 Method 1: Reduction of Oxygen-Containing Substituents 366
45.20.2.1.3.1.1 Variation 1: Reduction of Carbonyls 366
45.20.2.1.3.1.2 Variation 2: Reduction of Hydroxymethyl Groups 367
45.20.3 Product Subclass 3: [N]Phenylenes 367
45.20.3.1 Synthesis of Product Subclass 3 368
45.20.3.1.1 Synthesis by Ring-Closure Reactions 368
45.20.3.1.1.1 Method 1: Formation of Four- and Six-Membered Rings 368
45.20.3.1.1.1.1 Variation 1: Cobalt-Catalyzed Cyclization with an Alkyne 368
45.20.3.1.1.1.2 Variation 2: Cobalt-Catalyzed Cyclization with a Triyne 370
45.20.3.1.1.1.3 Variation 3: Cobalt-Catalyzed Intramolecular Cyclization 371
45.20.3.1.1.2 Method 2: Formation of a Six-Membered Ring by Cycloaddition 372
45.20.3.1.1.3 Method 3: Formation of Four-Membered Ring by Thermal Radical Coupling 373
45.20.3.1.2 Synthesis by Substitution 374
45.20.3.1.2.1 Method 1: Substitution of Silicon 374
45.21 Product Class 21: Phenanthrenes, Helicenes, and Other Angular Acenes 378
45.21.1 Product Subclass 1: Phenanthrenes and Benzo[c]phenanthrenes 379
45.21.1.1 Synthesis of Product Subclass 1 379
45.21.1.1.1 Synthesis by Intramolecular Cyclization Reactions 379
45.21.1.1.1.1 Method 1: Photodehydrocyclization of Stilbenes 379
45.21.1.1.1.2 Method 2: Photochemical Cyclization of Biaryl Aldehydes 381
45.21.1.1.1.3 Method 3: Friedel--Crafts Reactions 381
45.21.1.1.1.3.1 Variation 1: Friedel--Crafts Cycloalkylation 382
45.21.1.1.1.3.2 Variation 2: Friedel--Crafts Cycloacylation 382
45.21.1.1.1.3.3 Variation 3: Cyclization of Aromatic Nitriles 383
45.21.1.1.1.4 Method 4: Cyclization of 4-Arylquinol Ketals 383
45.21.1.1.1.5 Method 5: Homolytic Aromatic Substitution 385
45.21.1.1.1.5.1 Variation 1: The Pschorr Reaction 385
45.21.1.1.1.5.2 Variation 2: Tributyltin Hydride Mediated Radical Cyclization 385
45.21.1.1.1.6 Method 6: Oxidative Aryl Coupling 386
45.21.1.1.1.7 Method 7: The McMurry Reaction 387
45.21.1.1.1.8 Method 8: Ring-Closing Alkene Metathesis 388
45.21.1.1.1.9 Method 9: Directed Remote Metalation of Biaryls 388
45.21.1.1.1.10 Method 10: Cycloisomerization of Alkynylbiaryls 389
45.21.1.1.2 Syntheses Involving Intermolecular Cyclization Reactions 391
45.21.1.1.2.1 Method 1: Friedel--Crafts Acylation/Cycloalkylation 391
45.21.1.1.2.2 Method 2: Suzuki--Miyaura Coupling/Aldol Condensations 391
45.21.1.1.2.3 Method 3: Reactions of Arynes 392
45.21.1.1.2.3.1 Variation 1: Cycloadditions between Arynes and Furans 392
45.21.1.1.2.3.2 Variation 2: Cocyclization of Arynes and Allylic Halides 393
45.21.1.1.2.3.3 Variation 3: Cocyclization of Arynes and Halostyrenes 394
45.21.1.1.2.3.4 Variation 4: Cocyclization of Arynes and Alkynes 394
45.21.1.1.2.3.5 Variation 5: Cocyclization of Aryl Halides, Alkynes, and Arynes 395
45.21.1.1.2.4 Method 4: Cocyclization of Aromatic Halides and Alkynes 396
45.21.1.1.2.4.1 Variation 1: Cocyclization of Aryl Iodides and Alkynes 396
45.21.1.1.2.4.2 Variation 2: Cocyclization of Aryl Iodides and Alkynes in the Presence of Norbornene 397
45.21.1.1.2.4.3 Variation 3: Cocyclization of Iodobiaryls and Alkynes 397
45.21.1.1.2.4.4 Variation 4: Cocyclization of Diiodobiaryls and Alkynes 398
45.21.1.1.2.4.5 Variation 5: Chromium-Mediated Cocyclization between Halobiaryls and Alkynes 398
45.21.1.1.2.5 Method 5: Cocyclization between Chromium--Carbene Complexes and Alkynes 399
45.21.1.1.3 Synthesis by Other Processes 400
45.21.1.1.4 Synthesis of Nonracemic Benzo[c]phenanthrenes 401
45.21.1.1.4.1 Method 1: Resolution of Racemic 1,12-Dimethylbenzo[c]phenanthrene-5,8-dicarboxylic Acid 401
45.21.1.1.4.2 Method 2: Asymmetric Diels--Alder Cycloaddition/Aromatization 403
45.21.2 Product Subclass 2: Helicenes 403
45.21.2.1 Synthesis of Product Subclass 2 404
45.21.2.1.1 Synthesis by Intramolecular Cyclization Reactions with the Formation of One Ring 404
45.21.2.1.1.1 Method 1: Photodehydrocyclization of Stilbene-Type Precursors 404
45.21.2.1.1.2 Method 2: Ring-Closing Alkene Metathesis 408
45.21.2.1.1.3 Method 3: Carbenoid Coupling 410
45.21.2.1.1.4 Method 4: The McMurry Reaction 410
45.21.2.1.1.5 Method 5: Rearrangement of Benzannulated Enediynes 410
45.21.2.1.2 Synthesis by Intramolecular Cyclization Reactions with the Formation of Two Rings 411
45.21.2.1.2.1 Method 1: Photodehydrocyclization of 1,4-Bis(2-phenylvinyl)benzenes 411
45.21.2.1.2.2 Method 2: Friedel--Crafts Cycloacylation 414
45.21.2.1.2.3 Method 3: Friedel--Crafts Cycloalkylation 415
45.21.2.1.2.4 Method 4: Homolytic Aromatic Substitution 416
45.21.2.1.2.5 Method 5: C--H Arylation 418
45.21.2.1.3 Synthesis by Intramolecular Cyclization Reactions with the Formation of Three Rings 419
45.21.2.1.3.1 Method 1: Cycloisomerization of Dienetriynes 419
45.21.2.1.3.2 Method 2: Cycloisomerization of Triynes 422
45.21.2.1.4 Synthesis via Intermolecular Cyclization Reactions with the Formation of One Ring 426
45.21.2.1.4.1 Method 1: Diels--Alder Cycloadditions 426
45.21.2.1.5 Synthesis via Intermolecular Cyclization Reactions with the Formation of Two Rings 427
45.21.2.1.5.1 Method 1: Diels--Alder Cycloadditions 427
45.21.2.1.6 Synthesis by Other Processes 430
45.21.2.1.7 Synthesis of Nonracemic Helicenes 431
45.21.2.1.7.1 Method 1: Resolution of Racemic Helicen-1-ols 431
45.21.2.1.7.2 Method 2: Asymmetric Photodehydrocyclization 433
45.21.2.1.7.2.1 Variation 1: Diastereoselective Photodehydrocyclization Controlled by Internal Chiral Centers 433
45.21.2.1.7.2.2 Variation 2: Diastereoselective Photodehydrocyclization Controlled by External Chiral Centers 434
45.21.2.1.7.2.3 Variation 3: Stereoconservative Photodehydrocyclization Controlled via the Helical Unit 434
45.21.2.1.7.3 Method 3: Asymmetric Diels--Alder Cycloaddition/Aromatizations 435
45.21.2.1.7.4 Method 4: Diastereoselective Aromatic Oxy-Cope Rearrangements 436
45.21.2.1.7.5 Method 5: Enantioselective Cycloisomerization of Aromatic Triynes 436
45.21.2.1.7.6 Method 6: Enantioselective Cocyclization of Arynes and Alkynes 437
45.21.2.1.7.7 Method 7: Stereoconservative Cyclization of 1,1'-Binaphthalene-2,2'-diylbis(methylene)bis(triphenylphosphonium) Diperiodate 438
45.21.2.1.7.8 Method 8: Stereoconservative Stevens Rearrangements 439
45.21.3 Product Subclass 3: Other Angular Acenes 439
45.21.3.1 Synthesis of Product Subclass 3 439
45.22 Product Class 22: Pyrenes, Circulenes, and Other Condensed Acenes 448
45.22.1 Product Subclass 1: Pyrenes, Cyclopenta[cd]pyrenes, and Benzopyrenes 448
45.22.1.1 Synthesis of Product Subclass 1 449
45.22.1.1.1 Pyrenes 449
45.22.1.1.1.1 Method 1: Synthesis from [2.2]Metacyclophanes 449
45.22.1.1.1.1.1 Variation 1: Cycloaromatization 449
45.22.1.1.1.1.2 Variation 2: Cyclization and Aromatization of 8-Methoxy[2.2]metacyclophanes 449
45.22.1.1.1.2 Method 2: Synthesis from [2.2]Metacyclophane-1,9-dienes 450
45.22.1.1.1.3 Method 3: Lewis Acid Catalyzed Aromatization of [2.2]Metaparacyclophane-1,9-dienes 452
45.22.1.1.1.4 Method 4: Photocyclization and Aromatization of Biphenyl Derivatives 453
45.22.1.1.1.5 Method 5: Synthesis from 4-Ethynylphenanthrene Derivatives 454
45.22.1.1.2 Cyclopenta[cd]pyrene 455
45.22.1.1.2.1 Method 1: Flash-Vacuum Pyrolysis 455
45.22.1.1.2.1.1 Variation 1: Of 1-(1-Chlorovinyl)pyrene 455
45.22.1.1.2.1.2 Variation 2: Of 1,8-Bis(1-chlorovinyl)anthracene 455
45.22.1.1.2.2 Method 2: Synthesis via Cyclopenta[cd]pyren-3(4H)-one 456
45.22.1.1.3 Benzo[a]pyrene 457
45.22.1.1.3.1 Method 1: Oxidative Dehydrogenation of Dihydrobenzo[a]pyrenes 458
45.22.1.1.3.1.1 Variation 1: Synthesis via 11,12-Dihydrobenzo[a]pyrene 458
45.22.1.1.3.1.2 Variation 2: Synthesis via 9,10-Dihydrobenzo[a]pyrene 458
45.22.1.1.3.2 Method 2: Cyclodehydrogenation of a Biphenyl-Based Cyclophane 459
45.22.1.1.3.3 Method 3: Cyclization of 2-(2,6-Divinylphenyl)naphthalene Derivatives 459
45.22.1.1.3.4 Method 4: Dehydro-Diels--Alder Reaction of 1,8-Diethynylnaphthalene with Benzyne 461
45.22.1.1.4 Benzo[e]pyrene 461
45.22.1.1.4.1 Method 1: Synthesis from Pyrene 461
45.22.1.1.4.2 Method 2: Synthesis from Pyrene-4,5-dione 462
45.22.1.1.4.3 Method 3: Photocyclization of 4,5-Diphenylphenanthrene 462
45.22.1.1.4.4 Method 4: Synthesis from 7H-Benz[de]anthracene 463
45.22.1.1.5 Dibenzo[b,def]chrysene 464
45.22.1.1.5.1 Method 1: Synthesis via a Dodecahydrodibenzo[b,def]chrysene 464
45.22.1.1.5.2 Method 2: Cyclization of 1,5-Diarylnaphthalene Derivatives 465
45.22.1.1.6 Benzo[rst]pentaphene 466
45.22.1.1.6.1 Method 1: Synthesis via Dodecahydrobenzo[rst]pentaphene 466
45.22.1.1.6.2 Method 2: Cyclization of 1,4-Diarylnaphthalene Derivatives 467
45.22.1.1.7 Dibenzo[def,p]chrysenes 468
45.22.1.1.7.1 Method 1: Scholl Reaction of 1-Phenylbenz[a]anthracene Derivatives 468
45.22.1.1.7.2 Method 2: Cyclization of 7-Aryl-5,6-dihydro-4H-benz[de]anthracene Derivatives 469
45.22.1.1.7.3 Method 3: Cyclization of 12-Arylbenz[a]anthracene Derivatives 470
45.22.1.1.8 Dibenzo[fg,op]naphthacene 471
45.22.1.1.9 Dibenzo[c,mno]chrysene 471
45.22.1.1.10 Naphtho[8,1,2-ghi]chrysene 472
45.22.2 Product Subclass 2: Circulenes 472
45.22.2.1 Synthesis of Product Subclass 2 473
45.22.2.1.1 Dibenzo[ghi,mno]fluoranthene 473
45.22.2.1.1.1 Method 1: Flash-Vacuum Pyrolysis 473
45.22.2.1.1.2 Method 2: Solution-Phase Methods 475
45.22.2.1.2 Acenaphth[3,2,1,8-lmnoa]acephenanthrylene 477
45.22.2.1.2.1 Method 1: Synthesis from Fluoranthenes 477
45.22.2.1.3 8,9-Dihydroacenaphth[3,2,1,8-lmnoa]acephenanthrylene 478
45.22.2.1.3.1 Method 1: Synthesis from Dibenzo[ghi,mno]fluoranthenes 478
45.22.2.1.4 peri-Annulated Dibenzo[ghi,mno]fluoranthenes 478
45.22.2.1.4.1 Method 1: Synthesis from 1,10-Bis(bromomethyl)dibenzo[ghi,mno]fluoranthene 478
45.22.2.1.5 Benzo- and Dibenzo-Annulated Dibenzo[ghi,mno]fluoranthenes 479
45.22.2.1.6 Indeno-Annulated Dibenzo[ghi,mno]fluoranthenes 480
45.22.2.1.6.1 Method 1: Suzuki--Heck-Type Couplings 480
45.22.2.1.6.2 Method 2: Synthesis from Diynes and Alkynes 481
45.22.2.1.7 Coronene and Its Derivatives 482
45.22.2.1.7.1 Method 1: Synthesis from Benzo[ghi]perylene 482
45.22.2.1.7.2 Method 2: Synthesis from Anthracene Derivatives 482
45.22.2.1.7.3 Method 3: Dehydrocyclization of Cyclophanes 483
45.22.2.1.7.4 Method 4: Photocyclization of a Dienylcyclophane 484
45.22.2.1.8 Benzo[1,2,3-bc:4,5,6-b'c']dicoronene 484
45.22.2.1.9 Hexabenzo[bc,ef,hi,kl,no,qr]coronenes 485
45.22.2.1.9.1 Method 1: Lewis Acid Catalyzed Cyclodehydrogenation of Hexaarylbenzenes 485
45.22.2.1.10 Tribenzo[fgh,pqr,za1b1]trinaphthylenes 488
45.22.2.1.11 Peralkylated Coronenes 488
45.22.2.1.12 Dinaphtho[2,1,8,7-ghij:2',1',8',7'-nopq]pleiadene 489
45.22.2.1.12.1 Method 1: Cyclization of a Dialdehyde 489
45.22.2.1.12.2 Method 2: Flash-Vacuum Pyrolysis of a Cyclic Sulfone 490
45.22.2.1.13 Naphtho[2,1,8,7-ghij]naphtho[2',1',8',7':6,7,8]pleiadeno[10,11,12,1-nopqa]pleiadene 491
45.22.3 Product Subclass 3: Condensed Acenes 492
45.22.3.1 Synthesis of Product Subclass 3 492
45.22.3.1.1 Perylenes 492
45.22.3.1.1.1 Method 1: Thermal Decomposition of a Perylene Dianhydride 492
45.22.3.1.1.2 Method 2: Metal-Mediated Ullmann Reactions of 1,8-Dihalonaphthalenes 492
45.22.3.1.2 Benzo[a]perylene 493
45.22.3.1.3 Benzo[ghi]perylenes 494
45.22.3.1.3.1 Method 1: Synthesis from Perylene 494
45.22.3.1.3.2 Method 2: Ruthenium-Catalyzed Benzannulation 494
45.22.3.1.3.3 Method 3: Photocyclization 495
45.22.3.1.3.4 Method 4: Flash-Vacuum Pyrolysis 496
45.22.3.1.4 Dibenzo[a,e]perylene 496
45.22.3.1.5 Dibenzo[a,j]perylene 497
45.22.3.1.6 Dibenzo[cd,lm]perylene 498
45.22.3.1.6.1 Method 1: Dimerization of 1H-Phenalen-1-one 498
45.22.3.1.7 Naphtho[2,1-a]perylene 499
45.22.3.1.8 Tribenzo[de,kl,rst]pentaphene 499
45.22.3.1.9 Dibenzo[de,mn]naphthacene 500
45.22.3.1.10 Phenanthro[9,10-b]triphenylene 501
45.22.3.1.10.1 Method 1: Dehydrogenation of Octadecahydrophenanthro[9,10-b]triphenylene 501
45.22.3.1.10.2 Method 2: Zirconium-Mediated Coupling 502
45.22.3.1.10.3 Method 3: Palladium-Catalyzed [2 + 2 + 2] Cycloaddition 503
45.22.3.1.11 Benzo[c]naphtho[2,1-p]chrysenes 503
45.23 Product Class 23: Annulated Polycyclic Aromatic Hydrocarbons 510
45.23.1 Product Subclass 1: Acenaphthylenes 511
45.23.1.1 Synthesis of Product Subclass 1 511
45.23.1.1.1 Method 1: Synthesis from 1,2-Dihydroacenaphthylene Derivatives 511
45.23.1.1.2 Method 2: Synthesis from 1-Bromo- or 1,3-Dibromo-1H,3H-naphtho[1,8-cd]thiopyran 2,2-Dioxide 512
45.23.1.1.3 Method 3: Catalytic Annulation of Naphthalene Derivatives with Alkynes 513
45.23.2 Product Subclass 2: Cyclopent[fg]acenaphthylenes 515
45.23.2.1 Synthesis of Product Subclass 2 515
45.23.3 Product Subclass 3: Aceanthrylenes 515
45.23.3.1 Synthesis of Product Subclass 3 515
45.23.3.1.1 Method 1: Pyrolysis of 9-Ethynylanthracene 515
45.23.3.1.2 Method 2: Zirconium(IV)/Nickel(II)-Mediated Cycloadditions 516
45.23.3.1.3 Method 3: Palladium-Catalyzed Cycloaddition Reactions 516
45.23.4 Product Subclass 4: 1H-Phenalenes and Related Compounds 517
45.23.4.1 Synthesis of Product Subclass 4 517
45.23.4.1.1 Method 1: Synthesis of 1H-Phenalenes 517
45.23.4.1.1.1 Variation 1: By Dehydration of 2,3-Dihydro-1H-phenalen-1-ols 517
45.23.4.1.1.2 Variation 2: Via 1H-Phenalen-1-one 518
45.23.4.1.2 Method 2: Synthesis of Heteroatom-Substituted Phenalenes 519
45.23.4.1.2.1 Variation 1: Synthesis of Naphtho[1,8-bc]pyrans 519
45.23.4.1.2.2 Variation 2: Synthesis of 1-Methyl-1H-benzo[de]quinolines 520
45.23.4.1.3 Method 3: Synthesis of Cyclopenta[a]phenalenes 522
45.23.5 Product Subclass 5: Fluoranthenes 522
45.23.5.1 Synthesis of Product Subclass 5 522
45.23.5.1.1 Method 1: Diels--Alder Reaction 522
45.23.5.1.1.1 Variation 1: From Cyclopentadienone Derivatives 522
45.23.5.1.1.2 Variation 2: From Acenaphthylene 524
45.23.5.1.2 Method 2: Thermolytic Rearrangement of 1-(But-1-en-3-ynyl)-8-ethynylnaphthalenes 525
45.23.5.1.3 Method 3: Metal-Catalyzed C--C Bond-Forming Reactions 526
45.23.5.1.3.1 Variation 1: Palladium-Catalyzed Annulations 526
45.23.5.1.3.2 Variation 2: Rhodium-Catalyzed [(2 + 2) + 2] Cycloaddition 527
45.23.5.1.3.3 Variation 3: Tellurium-Mediated Cycloaromatization 528
45.23.6 Product Subclass 6: Benzo[j]fluoranthenes 529
45.23.6.1 Synthesis of Product Subclass 6 529
45.23.6.1.1 Method 1: Palladium-Catalyzed Annulation of Binaphthalenyl Trifluoromethanesulfonates 529
45.23.7 Product Subclass 7: Benzo[k]fluoranthenes 530
45.23.7.1 Synthesis of Product Subclass 7 530
45.23.7.1.1 Method 1: Synthesis from 1,8-Bis(diphenylethynyl)naphthalene 530
45.23.7.1.2 Method 2: Diels--Alder Reaction 530
45.23.7.1.3 Method 3: Palladium-Catalyzed Annulations 531
45.23.8 Product Subclass 8: Benz[e]acephenanthrylenes 531
45.23.8.1 Synthesis of Product Subclass 8 531
45.23.8.1.1 Method 1: Palladium-Catalyzed Annulation Reactions 531
45.23.8.1.1.1 Variation 1: From Phenanthrene Derivatives 531
45.23.8.1.1.2 Variation 2: From Fluorene Derivatives 532
45.23.8.1.2 Method 2: Base-Induced Cyclization of 9-(2-Bromobenzylidene)-9H-fluorene Derivatives 533
45.24 Product Class 24: Pentalenes, s-Indacenes, as-Indacenes, Azulenes, and Heptalenes, and Their Benzo Derivatives 536
45.24.1 Product Subclass 1: Pentalenes 537
45.24.1.1 Synthesis of Product Subclass 1 538
45.24.1.1.1 Pentalene Dimers 538
45.24.1.1.1.1 Method 1: Elimination of Hydrogen Bromide from 1-Bromo-1,2-dihydropentalene Followed by Dimerization 538
45.24.1.1.1.2 Method 2: Oxidative Coupling of Dilithium Pentalenediide 539
45.24.1.1.2 Benzopentalenes and Their Heteroatom Analogues 539
45.24.1.1.2.1 Method 1: Benzopentalenes by Flash-Vacuum Pyrolysis of Benzofurandiones 540
45.24.1.1.2.2 Method 2: 1H-Cyclopent[cd]indene by Gas-Phase Dehydrogenation/Decarboxylation 541
45.24.1.1.2.3 Method 3: 1H-Cyclopent[cd]indene by Gas-Phase Elimination of Acetic Acid 541
45.24.1.1.2.4 Method 4: 1H-Cyclopent[cd]indene by Flash-Vacuum Pyrolysis Induced Rearrangement of 1,2-Didehydronaphthalene 542
45.24.1.1.3 Dibenzopentalenes 542
45.24.1.1.3.1 Method 1: Dual Flash-Vacuum Pyrolysis of 1-Naphthylmethyl 3-Phenylprop-2-ynoate 542
45.24.1.1.3.2 Method 2: Rearrangement of Anthryl-9,10-dicarbenic Species 543
45.24.1.1.3.3 Method 3: Platinum(IV)-Catalyzed Ring Closure of 1,2-Bis(phenylethynyl)benzenes 543
45.24.1.1.3.4 Method 4: Tellurium-Mediated Chlorine Transfer 544
45.24.1.1.3.5 Method 5: Transition-Metal-Catalyzed Homocoupling of 1-Ethynyl-2-halobenzenes 545
45.24.1.1.3.6 Method 6: Carbolithiation of 5,6,11,12-Tetradehydrodibenzo[a,e]cyclooctene 547
45.24.2 Product Subclass 2: s-Indacenes 550
45.24.2.1 Synthesis of Product Subclass 2 550
45.24.2.1.1 1,3,5,7-Tetrasubstituted s-Indacenes and Their Heteroatom Analogues 550
45.24.2.1.1.1 Method 1: 1,3,5,7-Tetra-tert-butyl-s-indacene by Cyclocondensation 551
45.24.2.1.1.2 Method 2: 1,3,5,7-Tetra-tert-butyl-s-indacene by Acid-Catalyzed Condensation 551
45.24.3 Product Subclass 3: as-Indacenes 551
45.24.4 Product Subclass 4: Azulenes and Benzazulenes 553
45.24.4.1 Synthesis of Product Subclass 4 553
45.24.4.1.1 Azulenes 553
45.24.4.1.1.1 Method 1: Carbenoid [2 + 1]-Addition Reactions 553
45.24.4.1.1.1.1 Variation 1: Intermolecular Carbenoid Addition to a 4,7-Dihydroindane 553
45.24.4.1.1.1.2 Variation 2: Intramolecular Carbenoid Addition of (3-Aryl-3-bromopropanoyl)diazomethanes 554
45.24.4.1.1.1.3 Variation 3: Reaction of 4-Aryl-2-oxobutanoates with Lithium Diazo(trimethylsilyl)methane 556
45.24.4.1.1.2 Method 2: Ketene [2 + 2]-Addition Reactions 558
45.24.4.1.1.2.1 Variation 1: With 3-Chloroazulen-2(1H)-one as an Intermediate 558
45.24.4.1.1.2.2 Variation 2: Addition of Dichloroketene to 7-Methylcyclohepta-1,3,5-triene 559
45.24.4.1.1.2.3 Variation 3: With 1-Chloroazulenes as Intermediates 560
45.24.4.1.1.3 Method 3: [6 + 4]-Addition Reactions 561
45.24.4.1.1.3.1 Variation 1: Of 2-(Cyclopenta-2,4-dien-1-ylidene)-1,3-dioxolane and 2H-Pyran-2-one 561
45.24.4.1.1.3.2 Variation 2: Of a 6-Aminofulvene and Thiophene 1,1-Dioxides 562
45.24.4.1.1.3.3 Variation 3: Of Substituted Fulvenes and Thiophene 1,1-Dioxides 563
45.24.4.1.1.4 Method 4: [7 + 3]-Addition Reactions 564
45.24.4.1.1.5 Method 5: [8 + 2]-Addition Reactions 565
45.24.4.1.1.5.1 Variation 1: Reaction of Substituted Tropone Dimethyl Ketals with Dimethyl Acetylenedicarboxylate 565
45.24.4.1.1.5.2 Variation 2: Reaction of Highly Methylated 2H-Cyclohepta[b]furan-2-ones with Enol Ethers or Enamines 566
45.24.4.1.1.5.3 Variation 3: Thermal Intermolecular Reactions of 2H-Cyclohepta[b]furan-2-ones 568
45.24.4.1.1.5.4 Variation 4: Reactions of 2H-Cyclohepta[b]furan-2-ones with Vinyl Ethers, Acetals, Ortho Esters, or Their Analogues 569
45.24.4.1.1.5.5 Variation 5: Synthesis of Methyl (Azulen-2-yl)acetates 571
45.24.4.1.1.5.6 Variation 6: 2-Alkyl-3-cyanoazulene-1-carboxylic Acids as Precursors for 2-Alkylazulenes 571
45.24.4.1.1.6 Method 6: Transformation of Azulen-1(8aH)-ones into 1-Acetoxyazulenes 572
45.24.4.1.1.7 Method 7: Seven-Membered Ring Formation through a Robinson Annulation 573
45.24.4.1.1.8 Method 8: Five-Membered Ring Formation through an Intramolecular Wittig Reaction 573
45.24.4.1.1.8.1 Variation 1: Reaction of 5-[(Dimethylamino)methylene]cyclopenta-1,3-dienecarbaldehyde with an Allylidenephosphorane 574
45.24.4.1.1.8.2 Variation 2: Reaction of Dimethyl Acetylenedicarboxylate with [(Triphenylarsoranylidene)methyl]cycloheptatrienones 575
45.24.4.1.1.9 Method 9: Five-Membered Ring Formation through Nazarov Cyclization Reactions 575
45.24.4.1.1.10 Method 10: Ziegler--Hafner Synthesis of Deuterated Azulenes 577
45.24.4.1.1.11 Method 11: Methyl Azulene-2-carboxylates by the Hafner Method 577
45.24.4.1.1.12 Method 12: Conversion of 2-Arylazulene-1,1(8aH)-dicarbonitriles into 2-Arylazulene-1-carbonitriles 578
45.24.4.1.2 Benzazulenes 579
45.24.4.1.2.1 Method 1: Benz[a]azulenes by an Intramolecular Reaction of a Carbenoid 580
45.24.4.1.2.2 Method 2: Benz[a]azulenes by an Intramolecular Heck Reaction 580
45.24.4.1.2.3 Method 3: Benz[a]azulenes by Construction of the Benzo Ring 582
45.24.4.1.2.4 Method 4: Synthesis of Heteroatom Analogues of Benz[a]azulene 583
45.24.4.1.2.5 Method 5: Benz[cd]azulenes by the Buchner Reaction of Cyclopent[cd]azulenes 584
45.24.4.1.2.6 Method 6: Benz[cd]azulenes by Successive Formation of the Benzo Ring 584
45.24.4.1.2.7 Method 7: Alkylation of 4,5-Dihydro-3H-benz[cd]azulene To Give 9b-Methyl-9bH-benz[cd]azulene 585
45.24.5 Product Subclass 5: Heptalenes and Benzoheptalenes 585
45.24.5.1 Synthesis of Product Subclass 5 585
45.24.5.1.1 Heptalenes 585
45.24.5.1.1.1 Method 1: Hafner's Procedure 586
45.24.5.1.1.1.1 Variation 1: Reaction in Toluene 587
45.24.5.1.1.1.2 Variation 2: Reaction in Acetonitrile in the Presence of Dihydridotetrakis(triphenylphosphine)ruthenium 588
45.24.5.1.1.2 Method 2: Rearrangement of Dimethyl 11-Methyltricyclo[6.2.2.01,7]dodeca-2,4,6,9,11-pentaene-9,10-dicarboxylates 589
45.24.5.1.1.3 Method 3: Photochemical p-Bond Shift in Heptalene-4,5-dicarboxylates 590
45.24.5.1.1.4 Method 4: Thermal Rearrangement of Heptalene-4,5-dicarboxylates 591
45.24.5.1.2 Benzoheptalenes 592
45.24.5.1.2.1 Method 1: Decarboxylation of Dimethyl Benzo[a]heptalene-6,7-dicarboxylate 592
45.24.5.1.2.2 Method 2: Methoxy-Substituted Benzo[a]heptalenes from Colchiceines 593
45.24.5.1.2.3 Method 3: Thermal Reaction of Benz[a]azulenes with Acetylenedicarboxylates 594
45.24.5.1.2.4 Method 4: Alkylation of Heptalene-4,5-dicarboxylates with (Sulfonylmethyl)lithiums 595
45.24.5.1.2.4.1 Variation 1: Alkylation of Heptalene Lactones with [(Phenylsulfonyl)methyl]lithium 597
45.24.5.1.2.4.2 Variation 2: Alkylation of Methyl 4(5)-[(Phenylsulfonyl)acetyl]heptalene-5(4)-carboxylates with [(Phenylsulfonyl)methyl]lithium 597
45.24.5.1.2.5 Method 5: Diels--Alder Reaction of Heptaleno[1,2-c]furans with Electron-Deficient Alkenes 598
45.24.5.1.2.5.1 Variation 1: Reaction with (2E)-But-2-enedinitrile 598
45.24.5.1.2.5.2 Variation 2: Reaction with Dimethyl (2Z)-But-2-enedioate 600
45.24.5.1.2.5.3 Variation 3: Reaction with (Z)-1,2-Bis(phenylsulfonyl)ethene 600
45.24.5.1.2.6 Method 6: Benzo[a]heptalene-2,3-dicarboxylates by Electrocyclization 602
45.25 Product Class 25: Extended Polyaromatic Hydrocarbons: Graphite, Fullerene, and Carbon Nanotube Substructures 608
45.25.1 Product Subclass 1: Graphite Substructures and Graphene 608
45.25.1.1 Synthesis of Product Subclass 1 608
45.25.1.1.1 Synthesis of Graphite Substructures 608
45.25.1.1.1.1 Method 1: Intermolecular Fusion of Small Polycyclic Aromatic Hydrocarbon Building Blocks 611
45.25.1.1.1.2 Method 2: Intramolecular Oxidative Cyclodehydrogenation of Oligophenylenes 611
45.25.1.1.1.3 Method 3: Intramolecular Photodehydrocyclization 615
45.25.1.1.1.4 Method 4: Cyclodehydrogenation on Copper 616
45.25.1.1.2 Synthesis of Graphene 617
45.25.1.1.2.1 Method 1: Exfoliation from Highly Oriented Pyrolytic Graphite 617
45.25.1.1.2.2 Method 2: Synthesis from Silicon Carbide 618
45.25.1.1.2.3 Method 3: Oxidation of Graphite: The Graphene Oxide Approach 618
45.25.1.1.2.4 Method 4: Other Processes 618
45.25.2 Product Subclass 2: Fullerene Substructures 619
45.25.2.1 Synthesis of Product Subclass 2 619
45.25.2.1.1 Synthesis of Fullerenes 619
45.25.2.1.1.1 Method 1: Vaporization of Graphite 619
45.25.2.1.1.2 Method 2: Combustion 620
45.25.2.1.1.3 Method 3: Pyrolysis of Hydrocarbons 620
45.25.2.1.1.4 Method 4: Total Synthesis 620
45.25.2.1.1.4.1 Variation 1: Flash-Vacuum Pyrolysis 620
45.25.2.1.1.4.2 Variation 2: Cyclodehydrogenation on Platinum 621
45.25.2.1.2 Synthesis of Functionalized Fullerenes 622
45.25.2.1.3 Synthesis of Fullerene Substructures and Other Geodesic Polyarenes 624
45.25.2.1.3.1 Method 1: Flash-Vacuum Pyrolysis 625
45.25.2.1.3.2 Method 2: Intramolecular Palladium-Catalyzed Arylation 627
45.25.2.1.3.3 Method 3: Intramolecular Carbenoid Coupling 628
45.25.2.1.3.4 Method 4: Cyclodehydrogenation on Ruthenium 628
45.25.3 Product Subclass 3: Carbon Nanotube Substructures 628
45.25.3.1 Synthesis of Product Subclass 3 629
45.25.3.1.1 Synthesis of Carbon Nanotubes 629
45.25.3.1.1.1 Method 1: Electric-Arc Discharge of Graphite Electrodes 629
45.25.3.1.1.2 Method 2: Laser Ablation of Graphite 630
45.25.3.1.1.3 Method 3: Chemical Vapor Deposition 630
45.25.3.1.1.4 Method 4: Other Processes 630
45.25.3.1.2 Covalent Modification of Carbon Nanotubes 631
45.25.3.1.2.1 Method 1: Chemical Modification of Defect Sites 631
45.25.3.1.2.2 Method 2: Chemical Functionalization of the Carbon Nanotube Skeleton 632
45.26 Product Class 26: Triphenylenes, Tetraphenylenes, and Related Compounds 640
45.26.1 Product Subclass 1: Triphenylenes 640
45.26.1.1 Synthesis of Product Subclass 1 640
45.26.1.1.1 Method 1: Oxidative Trimerization of Benzene Derivatives 640
45.26.1.1.1.1 Variation 1: Oxidative Trimerization of 1,2-Dialkoxybenzenes 640
45.26.1.1.1.2 Variation 2: Trimerization of Catechol Ketals 642
45.26.1.1.2 Method 2: Oxidative Cyclization 644
45.26.1.1.2.1 Variation 1: Oxidative Addition of Benzene Derivatives to Biaryls 644
45.26.1.1.2.2 Variation 2: Oxidative Cyclization of o-Terphenyls 648
45.26.1.1.3 Method 3: Cyclization by Condensation Reaction 649
45.26.1.1.3.1 Variation 1: Metal-Mediated Ring Closure 649
45.26.1.1.3.2 Variation 2: Metal-Catalyzed Benzannulation of 2-Halobiphenyls 652
45.26.1.1.3.3 Variation 3: Metal-Catalyzed Trimerization of 2-(Trimethylsilyl)aryl Trifluoromethanesulfonates 654
45.26.1.1.4 Method 4: [4 + 2]-Cycloaddition Sequences 654
45.26.1.1.4.1 Variation 1: Conversion of Phencyclones 655
45.26.2 Product Subclass 2: Hydrotriphenylenes 657
45.26.2.1 Synthesis of Product Subclass 2 657
45.26.2.1.1 Method 1: Synthesis of 1,2,3,4,5,6,7,8,9,10,11,12-Dodecahydrotriphenylenes 657
45.26.2.1.1.1 Variation 1: Aldol Trimerization of Cyclohexanones 657
45.26.2.1.2 Method 2: Synthesis of Dihydrotriphenylenes 659
45.26.2.1.2.1 Variation 1: Synthesis of 1,2-Dihydrotriphenylene 659
45.26.2.1.2.2 Variation 2: Synthesis of 1,4-Dihydrotriphenylene 661
45.26.3 Product Subclass 3: Tetraphenylenes 661
45.26.3.1 Synthesis of Product Subclass 3 662
45.26.3.1.1 Method 1: Dimerization of Biphenylene Derivatives 662
45.26.3.1.1.1 Variation 1: Thermal Dimerization of Biphenylenes 662
45.26.3.1.1.2 Variation 2: Transition-Metal-Catalyzed Dimerization of Biphenylenes 663
45.26.3.1.2 Method 2: Oxidation of Dimetalated Derivatives 665
45.26.3.1.2.1 Variation 1: Oxidation of 1,2-Dimetalated Benzenes 665
45.26.3.1.2.2 Variation 2: Oxidation of 2,2'-Dimetalated Biphenyls 666
45.26.3.1.2.3 Variation 3: Mixed Oxidation of 2,2'-Dimetalated Biphenyls 669
45.26.3.1.3 Method 3: Cycloaddition with Dehydrobenzocyclooctene Derivatives 670
45.26.3.1.3.1 Variation 1: Cycloaddition of 2,3,4,5-Tetraphenylcyclopenta-2,4-dienone with Dehydrobenzocyclooctene Derivatives 671
45.26.3.1.3.2 Variation 2: Cycloaddition of Furans with Dehydrobenzocyclooctene Derivatives 671
45.26.4 Product Subclass 4: Higher Phenylenes 676
45.26.4.1 Synthesis of Product Subclass 4 677
45.26.4.1.1 Method 1: Oxidation of 2,2'-Dimetalated Biphenyls 677
45.26.4.1.1.1 Variation 1: Direct Oxidation of 2,2'-Dimetalated Biphenyls 677
45.26.4.1.1.2 Variation 2: Oxidation of 2,2'-Dimetalated Biphenyls via an Intermediate Chromate 679
45.26.4.1.2 Method 2: Cycloaddition Sequences with Dehydroannulenes 681
45.26.4.1.2.1 Variation 1: Benzannulation of Dehydroannulenes by Addition of Cyclopentadienones 681
45.27 Product Class 27: Calixarenes 686
45.27.1 Product Subclass 1: Calix[4]arenes 687
45.27.1.1 Synthesis of Product Subclass 1 687
45.27.1.1.1 Method 1: One-Step Synthesis 687
45.27.1.1.1.1 Variation 1: Base-Induced Reactions 687
45.27.1.1.1.2 Variation 2: Acid-Induced Reactions 689
45.27.1.1.2 Method 2: Functionalization Reactions 690
45.27.1.1.2.1 Variation 1: Substitution of Hydrogen 690
45.27.1.1.2.2 Variation 2: Substitution of tert-Butyl Groups 696
45.27.1.1.2.3 Variation 3: O-Demethylation 697
45.27.1.1.2.4 Variation 4: Substitution of Bromide 698
45.27.1.1.2.5 Variation 5: Substitution of Hydroxy Groups 700
45.27.1.1.2.6 Variation 6: Reduction of Nitro Groups 701
45.27.1.1.2.7 Variation 7: Protection of Phenolic Hydroxy Groups 703
45.27.2 Product Subclass 2: Calix[5]arenes 708
45.27.2.1 Synthesis of Product Subclass 2 708
45.27.2.1.1 Method 1: One-Step Synthesis 708
45.27.2.1.2 Method 2: Fragment Condensation Synthesis 708
45.27.2.1.2.1 Variation 1: [3 + 2]-Type Condensation 708
45.27.2.1.2.2 Variation 2: Linear-Type Condensation 709
45.27.2.1.3 Method 3: Functionalization Reactions 710
45.27.2.1.3.1 Variation 1: Substitution of Hydrogen 710
45.27.2.1.3.2 Variation 2: Substitution of tert-Butyl Groups 712
45.27.2.1.3.3 Variation 3: Substitution of Halogen 714
45.27.2.1.3.4 Variation 4: Reduction of Nitro Groups 717
45.27.2.1.3.5 Variation 5: Protection of Phenolic Hydroxy Groups 718
45.27.3 Product Subclass 3: Calix[6]arenes 719
45.27.3.1 Synthesis of Product Subclass 3 719
45.27.3.1.1 Method 1: One-Step Synthesis 719
45.27.3.1.2 Method 2: Functionalization Reactions 720
45.27.3.1.2.1 Variation 1: Substitution of Hydrogen 720
45.27.3.1.2.2 Variation 2: Substitution of tert-Butyl Groups 724
45.27.3.1.2.3 Variation 3: Reduction of Nitro Groups 726
45.27.3.1.2.4 Variation 4: Protection of Phenolic Hydroxy Groups 726
45.27.4 Product Subclass 4: Calix[7]arenes 730
45.27.4.1 Synthesis of Product Subclass 4 730
45.27.4.1.1 Method 1: One-Step Synthesis 730
45.27.4.1.2 Method 2: Functionalization Reactions 731
45.27.4.1.2.1 Variation 1: Substitution of tert-Butyl Groups 731
45.27.4.1.2.2 Variation 2: Protection of Phenolic Hydroxy Groups 733
45.27.5 Product Subclass 5: Calix[8]arenes 734
45.27.5.1 Synthesis of Product Subclass 5 734
45.27.5.1.1 Method 1: One-Step Synthesis 734
45.27.5.1.2 Method 2: Functionalization Reactions 735
45.27.5.1.2.1 Variation 1: Substitution of Hydrogen 735
45.27.5.1.2.2 Variation 2: Substitution of tert-Butyl Groups 739
45.27.5.1.2.3 Variation 3: Substitution of Nitro Groups 741
45.27.5.1.2.4 Variation 4: Protection of Phenolic Hydroxy Groups 741
45.27.6 Product Subclass 6: Calix[4]resorcinarene-4,6,10,12,16,18,22,24-octols 744
45.27.6.1 Synthesis of Product Subclass 6 744
45.27.6.1.1 Method 1: One-Step Synthesis 744
45.27.6.1.1.1 Variation 1: Acid-Induced Reactions 744
45.27.6.1.1.2 Variation 2: Base-Induced Reactions 745
45.27.6.1.2 Method 2: Functionalization Reactions 746
45.27.6.1.2.1 Variation 1: Substitution of Hydrogen 746
45.27.6.1.2.2 Variation 2: Substitution of Bromide 747
45.27.6.1.2.3 Variation 3: Protection of Phenolic Hydroxy Groups 749
45.27.7 Product Subclass 7: Homooxacalix[3]arene-25,26,27-triols 752
45.27.7.1 Synthesis of Product Subclass 7 752
45.27.7.1.1 Method 1: One-Step Synthesis 752
45.27.7.1.2 Method 2: Functionalization Reactions 753
45.27.7.1.2.1 Variation 1: Substitution of Bromide 753
45.27.7.1.2.2 Variation 2: Protection of Phenolic Hydroxy Groups 755
45.28 Product Class 28: Mononuclear Cyclophanes 760
45.28.1 Product Subclass 1: [n]Meta- and [n]Paracyclophanes 760
45.28.1.1 Synthesis of Product Subclass 1 760
45.28.1.1.1 Method 1: Construction of the Bridge by Acyloin Condensation 760
45.28.1.1.2 Method 2: Construction of the Bridge by Cross-Coupling Reactions with 1,.-Diorganometallic Species 761
45.28.1.1.2.1 Variation 1: Nickel-Catalyzed Cross Coupling with Di-Grignard Species (Kumada--Tamao Coupling) 761
45.28.1.1.2.2 Variation 2: Palladium-Catalyzed Cross Coupling with Diboryl Species (Suzuki--Miyaura Coupling) 762
45.28.1.1.3 Method 3: Construction of the Bridge by Cycloaddition 763
45.28.1.1.3.1 Variation 1: Reaction of Tetracyano-1,4-quinodimethane with Dicyclopropylethenes and Cyclopropylbutadienes 763
45.28.1.1.3.2 Variation 2: Reaction of Spirocyclic Cyclopropyl-Substituted Cyclohexadienes with Dienes 764
45.28.1.1.4 Method 4: Construction of the Bridge by Pyrolysis of Cyclic Sulfones 765
45.28.1.1.5 Method 5: Construction of the Bridge by Ring Contraction 769
45.28.1.1.6 Method 6: Construction of the Bridge by Hydrolysis of Furans 771
45.28.1.1.7 Method 7: Construction of the Aromatic Ring by Cycloaddition 771
45.28.1.1.7.1 Variation 1: Diels--Alder Reaction 771
45.28.1.1.7.2 Variation 2: Transition-Metal-Catalyzed Alkyne Cyclotrimerization 772
45.28.1.1.7.3 Variation 3: Palladium-Catalyzed Cycloaddition of Enynes 775
45.28.1.1.7.4 Variation 4: Cycloaddition of Fischer-Type Chromium--Carbene Complexes 777
45.28.1.1.8 Method 8: Construction of the Aromatic Ring by Rearrangement 778
45.28.1.1.8.1 Variation 1: Rearrangement of (Dibromocyclopropyl)carbinol-Containing [n.3.1]Propellanes 778
45.28.1.1.8.2 Variation 2: Rearrangement of Halogen-Substituted Unsaturated [n.3.1]Propellanes 779
45.28.1.1.8.3 Variation 3: Rearrangement of Dewar Benzene Type [n.2.2]Propellanes 780
45.28.1.1.8.4 Variation 4: Pyrolysis of a Tosylhydrazone Lithium Salt (Carbenoid Rearrangement) 783
45.28.2 Product Subclass 2: [n]Heterophanes 784
45.28.2.1 Synthesis of Product Subclass 2 784
45.28.2.1.1 Method 1: Synthesis by Paar--Knorr Reaction 784
45.28.2.1.2 Method 2: Synthesis by Nickel-Catalyzed Grignard Cyclocoupling 788
45.28.2.1.3 Method 3: Synthesis by Photoinduced Electron Transfer Promoted [3 + 2] Cycloaddition of Azirines 789
45.28.2.1.4 Method 4: Synthesis by Cobalt-Mediated [2 + 2 + 2] Cycloaddition of Diynes with Nitriles 790
45.28.2.1.5 Method 5: Synthesis by Ring Contraction Using Ruthenium(VIII) Oxide 791
45.28.3 Product Subclass 3: [n]Cyclophanes Containing Polycyclic Aromatic Rings 791
45.28.3.1 Synthesis of Product Subclass 3 791
45.28.3.1.1 Method 1: Synthesis by Acyloin Condensation 791
45.28.3.1.2 Method 2: Synthesis by Furan Hydrolysis 792
45.28.3.1.3 Method 3: Synthesis by Substitution of Dihaloalkanes 793
45.28.3.1.4 Method 4: Synthesis by Cycloaddition 795
45.28.3.1.5 Method 5: Synthesis by Rearrangement 798
45.29 Product Class 29: Polynuclear Cyclophanes 804
45.29.1 Product Subclass 1: Polynuclear Cyclophanes with Bridging Aliphatic Carbon Groups 806
45.29.1.1 Synthesis of Product Subclass 1 806
45.29.1.1.1 Method 1: Construction of the Bridge by Condensation Reactions 806
45.29.1.1.1.1 Variation 1: By Acyloin Condensation 806
45.29.1.1.1.2 Variation 2: By Aldol Condensation 808
45.29.1.1.1.3 Variation 3: By Wittig Reaction 809
45.29.1.1.1.4 Variation 4: By Alkene Metathesis 810
45.29.1.1.1.5 Variation 5: By McMurry Reaction 811
45.29.1.1.2 Method 2: Construction of the Bridge by Coupling Reactions 814
45.29.1.1.2.1 Variation 1: By Friedel--Crafts Reaction 814
45.29.1.1.2.2 Variation 2: By Wurtz Coupling 814
45.29.1.1.2.3 Variation 3: By Alkylation of an Active Methylene Group 815
45.29.1.1.2.4 Variation 4: By Coupling Using Tosylmethyl Isocyanide 816
45.29.1.1.3 Method 3: Construction of the Bridge by Addition Reactions 818
45.29.1.1.3.1 Variation 1: By Cycloaddition of p-Quinodimethanes 818
45.29.1.1.3.2 Variation 2: By Cycloaddition of o-Quinodimethanes 819
45.29.1.1.3.3 Variation 3: By Photochemical [2 + 2] Cycloaddition of Alkenes 820
45.29.1.1.3.4 Variation 4: By Acid-Catalyzed Addition of Alkenes 821
45.29.1.1.3.5 Variation 5: By C--H Insertion of a Carbene 822
45.29.1.1.3.6 Variation 6: By Insertion of Alkenes into the Bridge 822
45.29.1.1.4 Method 4: Construction of the Bridge by Extrusion of a Sulfur or Selenium Atom 823
45.29.1.1.4.1 Variation 1: By Thermal Extrusion of Sulfur Dioxide 823
45.29.1.1.4.2 Variation 2: By Photochemical Extrusion of Sulfur 825
45.29.1.1.4.3 Variation 3: By Wittig Rearrangement 826
45.29.1.1.4.4 Variation 4: By Stevens Rearrangement 827
45.29.1.1.4.5 Variation 5: By Extrusion of Selenium Atoms 829
45.29.1.1.5 Method 5: Construction of the Aromatic Ring 829
45.29.1.1.5.1 Variation 1: By Cyclotrimerization of Alkynes 829
45.29.1.1.5.2 Variation 2: By Valence Isomerization of Dewar Benzene Isomers 830
45.29.1.1.6 Method 6: Modification of the Aromatic Ring 831
45.29.1.1.6.1 Variation 1: By Annulation to the Aromatic Rings 831
45.29.1.1.6.2 Variation 2: By Oxidative Transformation of the Aromatic Rings 832
45.29.1.1.7 Method 7: Isomerization by Migration of the Bridge 832
45.29.2 Product Subclass 2: Polynuclear Cyclophanes without Bridging Aliphatic Carbon Groups 833
45.29.2.1 Synthesis of Product Subclass 2 833
45.29.2.1.1 Method 1: Cross Coupling of Aryl Halides 833
45.29.2.1.1.1 Variation 1: Oxidative Coupling of Arylene Di-Grignard Reagents 833
45.29.2.1.1.2 Variation 2: Coupling via Lipshutz Cuprates 835
45.29.2.1.1.3 Variation 3: Coupling of Arylstannanes Using Copper(II) Nitrate 836
45.29.2.1.2 Method 2: Construction of the Benzene Ring by Elimination 837
45.30 Product Class 30: Conjugated Polyenes, Including Cyclic Polyenes That Are Not Fully Conjugated 842
45.30.1 Product Subclass 1: Open-Chain Noncarotenoid Conjugated Polyenes 843
45.30.1.1 Synthesis of Product Subclass 1 843
45.30.1.1.1 Method 1: Palladium-Catalyzed Coupling Reactions 844
45.30.1.1.1.1 Variation 1: Stille Coupling 844
45.30.1.1.1.2 Variation 2: Negishi Coupling 848
45.30.1.1.1.3 Variation 3: Suzuki Coupling 849
45.30.1.1.1.4 Variation 4: Sonogashira Coupling 851
45.30.1.1.1.5 Variation 5: Heck Reaction 853
45.30.1.1.1.6 Variation 6: Silicon-Based Coupling 854
45.30.1.1.1.7 Variation 7: Homocoupling 855
45.30.1.1.2 Method 2: Rhodium-Catalyzed Coupling Reactions 856
45.30.1.1.3 Method 3: Nickel-Catalyzed Coupling Reactions 857
45.30.1.1.4 Method 4: Reductive Alkenation of Carbonyl Compounds 858
45.30.1.1.5 Method 5: Sulfone-Mediated Alkenation 858
45.30.1.1.5.1 Variation 1: Julia Alkenation 859
45.30.1.1.5.2 Variation 2: Julia--Kocienski Alkenation 861
45.30.1.1.6 Method 6: Wittig and Related Reactions 862
45.30.1.1.6.1 Variation 1: Wittig Reaction 863
45.30.1.1.6.2 Variation 2: Horner--Wadsworth--Emmons Modification 864
45.30.1.1.7 Method 7: Coupling with Vinylic Organolithium Reagents 865
45.30.1.1.8 Method 8: Lewis Acid Promoted Coupling Reactions 867
45.30.1.1.9 Method 9: Ramberg--Bäcklund Rearrangement 869
45.30.1.1.10 Method 10: Oxidative Ring-Fragmentation Reactions 870
45.30.1.1.11 Method 11: Cyclopropyl Carbinol Rearrangement 872
45.30.1.2 Applications of Product Subclass 1 in Organic Synthesis 872
45.30.1.2.1 Method 1: Lewis Acid Catalyzed Cycloisomerization of Hexatriene 872
45.30.1.2.2 Method 2: Thermal Electrocyclization of Hexatriene 873
45.30.2 Product Subclass 2: Carotenoid Compounds 874
45.30.2.1 Synthesis of Product Subclass 2 874
45.30.2.1.1 Method 1: Palladium-Catalyzed Coupling Reactions 875
45.30.2.1.1.1 Variation 1: Stille Coupling 875
45.30.2.1.1.2 Variation 2: Negishi Coupling 878
45.30.2.1.1.3 Variation 3: Suzuki Coupling 879
45.30.2.1.2 Method 2: Reductive Alkenation of Carbonyl Compounds 881
45.30.2.1.3 Method 3: Sulfone-Mediated Alkenation 882
45.30.2.1.3.1 Variation 1: Julia Alkenation 882
45.30.2.1.3.2 Variation 2: Julia--Kocienski Alkenation 884
45.30.2.1.3.3 Variation 3: Reaction with 3-Sulfolenes 886
45.30.2.1.3.4 Variation 4: Double Elimination Reaction 887
45.30.2.1.4 Method 4: Wittig Reaction 889
45.30.2.1.5 Method 5: Extended Knoevenagel Condensation 891
45.30.2.1.6 Method 6: Ramberg--Bäcklund Rearrangement 893
45.30.3 Product Subclass 3: Cycloheptatrienes 895
45.30.3.1 Synthesis of Product Subclass 3 895
45.30.3.1.1 Method 1: Transition-Metal-Mediated [3 + 2 + 2]-Cycloaddition Reaction 895
45.30.3.1.1.1 Variation 1: Palladium-Catalyzed Cycloaddition 895
45.30.3.1.1.2 Variation 2: Nickel-Mediated Cycloaddition 896
45.30.3.1.2 Method 2: Rhodium-Catalyzed Addition of Diazo Compounds 898
45.30.3.1.3 Method 3: Addition to a Tropylium Salt 899
45.30.3.1.3.1 Variation 1: Using Organolithium Reagents 899
45.30.3.1.3.2 Variation 2: Using Hetero Nucleophiles 900
45.30.3.1.3.3 Variation 3: Using Reactive Alkenes 903
45.30.3.1.3.4 Variation 4: Using Reactive Alkanes 905
45.30.3.1.4 Method 4: Ring-Expansion Reactions 906
45.31 Product Class 31: Macromolecular Conjugated Polyenes 914
45.31.1 Product Subclass 1: Polyacetylene 914
45.31.1.1 Synthesis of Product Subclass 1 914
45.31.1.1.1 Method 1: Polymerization by the Shirakawa Method 914
45.31.1.1.2 Method 2: Polymerization by the Naarmann Method 915
45.31.2 Product Subclass 2: Monosubstituted Aromatic Acetylene Polymers 916
45.31.2.1 Synthesis of Product Subclass 2 916
45.31.2.1.1 Method 1: Polymerization Using Rhodium Catalysts 916
45.31.2.1.2 Method 2: Polymerization Using Tungsten Catalysts 919
45.31.2.1.3 Method 3: Polymerization Using Molybdenum Catalysts 921
45.31.3 Product Subclass 3: Monosubstituted Aliphatic Acetylene Polymers 922
45.31.3.1 Synthesis of Product Subclass 3 922
45.31.3.1.1 Method 1: Polymerization Using Rhodium Catalysts 922
45.31.4 Product Subclass 4: Disubstituted Aromatic Acetylene Polymers 925
45.31.4.1 Synthesis of Product Subclass 4 925
45.31.4.1.1 Method 1: Polymerization Using Tantalum Catalysts 925
45.31.4.1.2 Method 2: Polymerization Using Molybdenum Catalysts 927
45.31.5 Product Subclass 5: Disubstituted Aliphatic Acetylene Polymers 928
45.31.5.1 Synthesis of Product Subclass 5 929
45.31.5.1.1 Method 1: Polymerization Using Tantalum Catalysts 929
45.31.5.1.2 Method 2: Polymerization Using Molybdenum Catalysts 930
Keyword Index 934
Author Index 990
Abbreviations 1028