Preface ...................................................... ХIII
List of Contributors ........................................... XV
1 Arylation Reactions: A Historical Perspective ................ 1
Lutz Ackermann
1.1 Structure and Bonding of Benzene ........................ 1
1.2 Syntheses of Substituted (Hetero)Arenes, and
the Contents of this Book ............................... 3
Abbreviations .......................................... 18
References ............................................. 18
2 Metal-Catalyzed Coupling Reactions with Aryl Chlorides,
Tosylates and Fluorides ..................................... 25
Adam Littke
2.1 Introduction ........................................... 25
2.2 Coupling Reactions of Aryl Chlorides ................... 26
2.2.1 Nickel-Catalyzed Cross-Couplings of Aryl
Chlorides ....................................... 27
2.2.2 Palladium-Catalyzed Cross-Coupling Reactions .... 29
2.2.2.1 Suzuki Reaction ........................ 29
2.2.2.2 Stille Reaction ........................ 42
2.2.2.3 Hiyama Coupling ........................ 45
2.2.2.4 Negishi Coupling ....................... 49
2.2.2.5 Kumada Coupling ........................ 51
2.3 Coupling Reactions of Aryl Fluorides ................... 53
2.4 Coupling Reactions of Aryl Tosylates ................... 56
2.5 Conclusions ............................................ 59
Abbreviations .......................................... 60
References ............................................. 61
3 Palladium-Catalyzed Arylations of Amines and α-C-H Acidic
Compounds ................................................... 69
Björn Schlummer and Ulrich Scholz
3.1 Introduction ........................................... 69
3.2 Palladium-Catalyzed Arylations of Amines ............... 70
3.2.1 Historical Development .......................... 70
3.2.2 Catalytic Systems ............................... 72
3.2.2.1 Palladium Sources ...................... 73
3.2.2.2 Ligands ................................ 73
3.2.2.3 Bases .................................. 83
3.2.2.4 Solvents ............................... 84
3.2.3 Aryl Halides .................................... 85
3.2.4 Arylsulfonic Acid Esters ........................ 86
3.2.5 Heteroaromatic Electrophiles .................... 87
3.2.6 Amines as Nucleophiles .......................... 89
3.2.7 Amine Derivatives as Nucleophiles ............... 90
3.2.8 Applications .................................... 92
3.2.9 Mechanistic Aspects ............................. 94
3.2.10 Chirality ....................................... 95
3.3 Palladium-Catalyzed Arylations of α-C-H Acidic
Compounds .............................................. 96
3.3.1 Historical Development .......................... 96
3.3.2 Catalytic Systems ............................... 98
3.3.3 α-Arylations of Esters .......................... 98
3.3.4 α-Arylations of Malonates and α-Cyano Esters ... 202
3.3.5 α-Arylations of Ketones ........................ 103
3.3.6 α-Arylations of Amides ......................... 104
3.3.7 α-Arylations of Nitriles ....................... 106
3.4 Summary and Conclusions ............................... 109
Abbreviations ......................................... 111
References ............................................ 112
4 Copper-Catalyzed Arylations of Amines and Alcohols with
Boron-Based Arylating Reagents ............................. 121
Andrew W. Thomas and Steven V. Ley
4.1 Introduction .......................................... 121
4.2 Discovery and Development of a New O-H Bond
Arylation Reaction: From Stoichiometric to Catalytic
in Copper ............................................. 123
4.3 Mechanistic Considerations ............................ 125
4.4 Miscellaneous Applications ............................ 127
4.4.1 Additional Applications with ArB(OH)2 .......... 127
4.4.2 Alternatives to ArB(OH)2 ....................... 128
4.4.3 Alternatives to Phenols ........................ 131
4.5 Development of a New N-H Bond Arylation Reaction ...... 132
4.5.1 Stoichiometric in Copper ....................... 132
4.5.2 Alternatives to Boronic Acids .................. 138
4.6 Development of a New N-H Bond Arylation Reaction:
Catalytic in Copper ................................... 138
4.6.1 Proposed Mechanism ............................. 140
4.6.2 Additional Important Non-N-H Arylation
Examples ....................................... 147
4.7 Summary and Conclusions ............................... 149
Abbreviations ......................................... 151
References ............................................ 152
5 Metal-Catalyzed Arylations of Nonactivated Alkyl
(Pseudo)Halides via Cross-Coupling Reactions ............... 155
Masaharu Nakamura and Shingo Ito
5.1 Introduction .......................................... 155
5.2 Palladium-Catalyzed Arylations of Alkyl
(Pseudo)Halides ....................................... 156
5.3 Nickel-Catalyzed Arylations of Alkyl
(Pseudo)Halides ....................................... 163
5.4 Iron-Catalyzed Arylations of Alkyl (Pseudo)Halides .... 168
5.5 Copper- and Cobalt-Catalyzed Arylations of Alkyl
(Pseudo)Halides ....................................... 174
Abbreviations ......................................... 179
References ............................................ 179
6 Arylation Reactions of Alkynes: The Sonogashira Reaction ... 183
Mihai S. Viciu and Steven P. Nolan
6.1 Introduction .......................................... 183
6.2 Palladium-Catalyzed Reactions: Ligands and Reaction
Protocols ............................................. 185
6.2.1 Phosphine-Based Ligands ........................ 185
6.2.1.1 Copper-Free Catalytic Systems ......... 186
6.2.1.2 Hemilabile Ligands .................... 188
6.2.1.3 Ionic Liquids as Reaction Media ....... 190
6.2.1.4 Reactions in Aqueous Media ............ 190
6.2.1.5 Recyclable Phosphine-Based Catalytic
Systems ............................... 191
6.2.2 N-Heterocyclic Carbene Ligands for
Sonogashira Coupling ........................... 192
6.2.3 Palladacycles as Catalysts in Sonogashira
Reactions ...................................... 197
6.2.4 Nitrogen-Coordinating Ligands .................. 199
6.3 Alternative Metal Catalysts ........................... 205
6.3.1 Nickel-Catalyzed Sonogashira Reaction .......... 205
6.3.2 Ruthenium-Based Catalytic Systems .............. 206
6.3.3 Indium-Based Catalytic Systems ................. 207
6.3.4 Copper-Based Catalytic Systems ................. 207
6.4 Mechanism of the Sonogashira Reaction ................. 208
6.4.1 Palladium- and Copper-Based Catalytic
Systems ........................................ 209
6.4.2 Copper-Free Catalytic Systems .................. 210
6.5 Concluding Remarks .................................... 214
Abbreviations ......................................... 215
References ............................................ 216
7 Palladium-Catalyzed Arylation Reactions of Alkenes
(Mizoroki-Heck Reaction and Related Processes) ............. 221
Verena T. Trepohl and Martin Oestreich
7.1 Introduction .......................................... 221
7.2 Mizoroki-Heck Arylations .............................. 222
7.2.1 Mechanistic Considerations ..................... 222
7.2.2 Intermolecular Mizoroki-Heck Arylations ........ 225
7.2.2.1 Intermolecular Arylations ............. 225
7.2.2.2 Asymmetric Intermolecular
Arylations ............................ 232
7.2.2.3 Directed Intermolecular Arylations .... 235
7.2.3 Intramolecular Mizoroki-Heck Arylations ........ 239
7.2.3.1 Intramolecular Arylations ............. 239
7.2.3.2 Asymmetric Intramolecular
Arylations ............................ 239
7.2.3.3 Desymmetrizing Intramolecular
Arylations ............................ 236
7.3 Reductive Mizoroki-Heck-Type Arylations ............... 248
7.3.1 Mechanistic Considerations ..................... 249
7.3.2 Intermolecular Arylations: The
Bicyclo[2.2.1]heptane Case ..................... 250
7.3.3 Reductive Mizoroki-Heck-Type Arylation in
Action ......................................... 252
7.4 Oxidative Mizoroki-Heck-Type Arylations ............... 254
7.4.1 Mechanistic Considerations ..................... 254
7.4.2 Intermolecular C-C Bond Formation .............. 255
7.4.2.1 Arenes as Nucleophiles ................ 255
7.4.2.2 Hetarenes as Nucleophiles ............. 256
7.4.3 Intramolecular C-C Bond Formation .............. 259
7.4.3.1 Arenes as Nucleophiles ................ 259
7.4.3.2 Hetarenes as Nucleophiles ............. 261
Abbreviations ......................................... 264
References ............................................ 264
8 Modern Arylations of Carbonyl Compounds .................... 271
Christian Defieber and Erick M. Carreira
8.1 Introduction .......................................... 271
8.2 Enantioselective Arylation of Aldehydes ............... 271
8.2.1 Zinc-Mediated Asymmetric Arylation of
Aldehydes ...................................... 271
8.2.2 Rhodium-Catalyzed Asymmetric Arylation of
Aldehydes ...................................... 274
8.3 Enantioselective Arylation of Ketones ................. 276
8.3.1 Enantioselective Arylation of Aryl-Alkyl-
Substituted Ketones ............................ 276
8.3.2 Enantioselective Arylation of Isatins .......... 277
8.3.3 Enantioselective Arylation of
Trifluoromethyl-Substituted Ketones ............ 277
8.4 Enantioselective Arylation of Imines .................. 278
8.4.1 Zinc-Mediated Enantioselective Phenylation of
Imines ......................................... 278
8.4.2 Rhodium-Catalyzed Enantioselective Arylation
of Imines ...................................... 279
8.4.3 Rhodium-Catalyzed Diastereoselective
Arylation of Imines ............................ 280
8.5 Conjugate Asymmetric Arylation ........................ 281
8.5.1 Aryl Sources for the Conjugate Asymmetric
Arylation ...................................... 281
8.5.2 Ligand Systems ................................. 282
8.5.3 Conjugate Arylation with Diphosphine-
Palladium(II) Complexes ........................ 284
8.5.4 Enantioselective Conjugate Arylation of
α,β-Unsaturated Aldehydes ...................... 285
8.5.5 Enantioselective Conjugate Arylation of
Maleimides ..................................... 286
8.5.6 Additional Acceptors for Rhodium/Diene-
Catalyzed Conjugate Arylation .................. 288
8.5.7 Enantioselective Conjugate Arylation of
2,3-Dihydro-4-Pyridones ........................ 289
8.5.8 Enantioselective Conjugate Arylation of
Coumarins ...................................... 290
8.5.9 Conjugate Arylation of Chiral, Racemic
α,β-Unsaturated Carbonyl Compounds ............. 290
8.5.10 Conjugate Asymmetric Arylation of
3-Substituted α,β-unsarurated Carbonyl
Compounds ...................................... 291
8.5.11 1,6-Addition of Arylboronic Acids to α,β. γ
δ-Unsaturated Carbonyl Compounds ............... 291
8.6 Tandem Processes ...................................... 293
8.6.1 Rhodium-Catalyzed Enantioselective Conjugate
Arylation-Protonation .......................... 293
8.6.2 Rhodium-Catalyzed Conjugate Arylation-Aldol-
Addition ....................................... 295
8.6.3 Rhodium-Catalyzed Conjugate Arylation-
Allylation ..................................... 296
8.6.4 Rhodium-Catalyzed Sequential
Carbometallation-Addition ...................... 296
8.7 Enantioselective Friedel-Crafts Arylation ............. 298
8.7.1 Metal-Catalyzed Enantioselective Friedel-
Crafts Arylations .............................. 298
8.7.2 Organocatalysis in Friedel-Crafts Arylation .... 300
8.8 Conclusions ........................................... 303
Abbreviations ......................................... 304
References ............................................ 304
9 Metal-Catalyzed Direct Arylations (excluding Palladium) .... 311
Lutz Ackermann and Rubén Vicente
9.1 I ntroduction ......................................... 311
9.2 Rhodium-Catalyzed Direct Arylations ................... 312
9.2.1 Rhodium-Catalyzed Direct Arylations of
Arenes ......................................... 312
9.2.2 Rhodium-Catalyzed Direct Arylations of
Heteroarenes ................................... 317
9.3 Ruthenium-Catalyzed Direct Arylations ................. 320
9.3.1 Ruthenium-Catalyzed Direct Arylations with
Organometallic Reagents ........................ 320
9.3.2 Ruthenium-Catalyzed Direct Arylations with
Aryl (Pseudo) Halides .......................... 322
9.4 Iridium-, Copper- and Iron-Catalyzed Direct
Arylations ............................................ 327
9.5 Conclusions ........................................... 330
Abbreviations ......................................... 330
References ............................................ 331
10 Palladium-Catalyzed Direct Arylation Reactions ............. 335
Masahiro Miura and Tetsuya Satoh
10.1 Introduction .......................................... 335
10.2 Intermolecular Arylation of Functionalized Arenes ..... 337
10.2.1 Reaction of Phenols and Benzyl Alcohols ........ 337
10.2.2 Reaction of Aromatic Carbonyl and Pyridyl
Compounds ...................................... 341
10.2.3 Reaction of Miscellaneous Aromatic
Substrates ..................................... 345
10.3 Intramolecular Reaction of Haloaryl-Linked Arenes ..... 346
10.4 Intermolecular Arylation Reactions of Heteroaromatic
Compounds ............................................. 348
10.4.1 Reaction of Pyrroles, Furans and Thiophenes .... 348
10.4.2 Reaction of Imidazoles, Oxazoles and
Thiazoles ...................................... 353
10.4.3 Reaction of Six-Membered Nitrogen
Heterocycles ................................... 356
10.5 Concluding Remarks .................................... 357
Abbreviations ......................................... 358
References ............................................ 358
11 Mechanistic Aspects of Transition Metal-Catalyzed Direct
Arylation Reactions ........................................ 363
Paula de Mendoza and Antonio M. Echavarren
11.1 Introduction .......................................... 363
11.2 Palladium-Catalyzed Intramolecular Direct Arylation ... 363
11.3 Intermolecular Metal-Catalyzed Direct Arylation of
Arenes ................................................ 372
11.4 Metal-Catalyzed Heteroaryl-Aryl and Heteroaryl-
Heteroaryl Bond Formation ............................. 374
11.5 Direct Arylation via Metallacycles .................... 380
11.6 Cross-Dehydrogenative Couplings ....................... 388
11.7 Summary ............................................... 391
Abbreviations ......................................... 391
References ............................................ 392
12 Arylation Reactions Involving the Formation of Arynes ...... 401
Yu Chen and Richard С. Larock
12.1 Introduction .......................................... 401
12.2 Generation of Arynes .................................. 402
12.3 Electrophilic Coupling of Arynes ...................... 404
12.3.1 Formation of Monosubstituted Arenes by Proton
Abstraction .................................... 405
12.3.2 Aryne Insertion into a Nucleophilic-
Electrophilic o-Bond ........................... 410
12.3.3 Three-Component Coupling Reactions via Aryl
Carbanion Trapping by an External
Electrophile ................................... 417
12.3.4 Miscellaneous .................................. 422
12.4 Pericyclic Reactions of Arynes ........................ 427
12.4.1 Diels-Alder Reactions .......................... 427
12.4.2 [2+2] Cycloadditions ........................... 441
12.4.3 [3+2] Cycloadditions ........................... 443
12.4.1 Ene Reaction ................................... 446
12.4.5 Miscellaneous .................................. 447
12.5 Transition Metal-Catalyzed Reactions of Arynes ........ 449
12.5.1 Transition Metal-Catalyzed Cyclizations ........ 449
12.5.1.1 Palladium/Nickel-Catalyzed [2+2+2]
Cycloadditions ........................ 449
12.5.1.2 Palladium-Catalyzed Cyclization
Involving Carbopalladation of
Arynes ................................ 457
12.5.1.3 Transition Metal-Catalyzed
Carbonylations ........................ 461
12.5.1.4 Miscellaneous ......................... 462
12.5.2 Transition Metal-Catalyzed Coupling
Reactions ...................................... 462
12.5.2.1 Insertion of Arynes into a-Bonds ...... 462
12.5.2.2 Three-Component Coupling of Arynes
Involving Carbopalladation ............ 465
12.6 Summary ............................................... 468
Abbreviations ......................................... 468
References ............................................ 469
13 Radical-Based Arylation Methods ............................ 475
Santiago E. Vaillard, Birte Schulte and Armido Studer
13.1 Introduction .......................................... 475
13.2 SRN1-Type Radical Arylations .......................... 475
13.2.1 Intermolecular SRN1 Reactions .................. 476
13.2.2 Intramolecular SRN1 Reactions .................. 479
13.3 Homolytic Aromatic Substitutions ...................... 480
13.3.1 Intramolecular Homolytic Aromatic
Substitutions .................................. 480
13.3.1.1 Arylations Using Nucleophilic
C-Centered Radicals ................... 480
13.3.1.2 Arylations Using Electrophilic
C-Centered Radicals ................... 485
13.3.1.3 Radical Aryl Migration Reactions ...... 486
13.3.2 Intermolecular Homolytic Aromatic
Substitutions .................................. 489
13.3.2.1 Arylation with Nucleophilic
C-Centered Radicals ................... 489
13.3.2.2 Arylation with Electrophilic
C-Centered Radicals ................... 493
13.3.2.3 Intermolecular ipso-Substitutions ..... 495
13.4 Arylations Using Aryl Radicals ........................ 496
13.4.1 Additions onto Olefins: Meerwein Arylation ..... 496
13.4.2 Cyclizations Using Aryl Radicals ............... 498
13.4.3 Phosphonylation of Aryl Radicals ............... 502
13.5 Conclusions ........................................... 502
Abbreviations ......................................... 503
References ............................................ 503
14 Photochemical Arylation Reactions .......................... 513
Valentino Dichiarante, Maurizio Fagnoni and Angelo Albini
14.1 Introduction .......................................... 513
14.2 Photochemical Formation of Aryl-C Bonds ............... 517
14.2.1 Intermolecular Formation of Aryl-Alkyl Bonds ... 517
14.2.2 Cyanations ..................................... 525
14.2.3 Intramolecular Formation of Aryl-Alkyl Bonds ... 526
14.2.4 Intermolecular Formation of Aryl-Aryl Bonds .... 527
14.2.5 Intramolecular Formation of Aryl-Aryl Bonds .... 529
14.3 Photochemical Formation of Aryl-N Bonds ............... 530
14.4 Conclusions ........................................... 532
Abbreviations ......................................... 532
References ............................................ 532
Index ......................................................... 537
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