Arene chemistry: reaction mechanisms and methods for aromatic compounds (Hoboken, 2016). - ОГЛАВЛЕНИЕ / CONTENTS
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ОбложкаArene chemistry: reaction mechanisms and methods for aromatic compounds / ed. by J.Mortier. - Hoboken: Wiley, 2016. - xxvii, 959 p.: ill., tab. - Bibliogr. at the end of the chapters. - Ind.: p.939-959. - ISBN 978-1-118-75201-2
Шифр: (И/Г2-А73) 02
 

Место хранения: 02 | Отделение ГПНТБ СО РАН | Новосибирск

Оглавление / Contents
 
LIST OF CONTRIBUTORS .......................................... xxi
PREFACE ....................................................... xxv

PART I  ELECTROPHILIC AROMATIC SUBSTITUTION

1    Electrophilic Aromatic Substitution: Mechanism ............. 3
     Douglas A. Klumpp
1.1  Introduction ............................................... 3
1.2  General Aspects ............................................ 4
1.3  Electrophiles .............................................. 4
1.4  Arene Nucleophiles ........................................ 12
1.5  π-Complex Intermediates ................................... 17
1.6  σ-Complex or Wheland Intermediates ....................... 22
1.7  Summary and Outlook ....................................... 27
     Abbreviations ............................................. 27
     References ................................................ 28

2    Friedel-Crafts Alkylation of Arenes in Total Synthesis
     Gonzalo Blay, Marc Montesinos-Magraner and José R. Pedro
2.1  Introduction .............................................. 33
2.2  Total Synthesis Involving Intermolecular FC Alkylations ... 34
     2.2.1  Synthesis of Coenzyme Q  ........................... 34
     2.2.2  Total Synthesis of (±)-Brasiliquinone B ............ 35
     2.2.3  Synthesis of (-)-Podophyllotoxin ................... 35
     2.2.4  Synthesis of Puupehenol and Related Compounds ...... 36
     2.2.5  Synthesis of (-)-Talaumidin ........................ 36
     2.2.6  Total Synthesis of (±)-Schefferine ................. 37
2.3  Total Synthesis Involving Intramolecular FC Alkylations ... 37
     2.3.1  С-С Bond Formation Leading to Homocyclic Rings ..... 37
     2.3.2  С-С Bond Formation Leading to Oxygen-Containing
            Rings .............................................. 43
     2.3.3  С-С Bond Formation Leading to Nitrogen-Containing
            Rings .............................................. 44
2.4  Total Synthesis Through Tandem and Cascade Processes
     Involving FC Reactions .................................... 46
     2.4.1  С-С Bond Formation Leading to Homocyclic Rings ..... 46
     2.4.2  С-С Bond Formation Leading to Oxygen-Containing
            Rings .............................................. 49
     2.4.3  С-С Bond Formation Leading to Nitrogen-Containing
            Rings .............................................. 52
2.5  Total Synthesis Involving ipso-FC Reactions ............... 54
     2.5.1  Synthesis of (S)-(-)-Xylopinine .................... 54
     2.5.2  Synthesis of Garcibracteatone ...................... 55
2.6  Summary and Outlook ....................................... 56
2.7  Acknowledgment ............................................ 56
     Abbreviations ............................................. 56
     References ................................................ 57

3    Catalytic Friedel-Crafts Acylation Reactions .............. 59
     Giovanni Sartori, Raimondo Maggi and Veronica Santacroce
3.1  Introduction and Historical Background .................... 59
3.2  Catalytic Homogeneous Acylations .......................... 60
     3.2.1  Metal Halides ...................................... 60
     3.2.2  Perfluoroalkanoic Acids Perfluorosulfonic Acids
            and Their (Metal) Derivatives ...................... 62
     3.2.3  Miscellaneous ...................................... 63
3.3  Catalytic Heterogeneous Acylations ........................ 64
     3.3.1  Zeolites ........................................... 64
     3.3.2  Clays .............................................. 69
     3.3.3  Metal Oxides ....................................... 70
     3.3.4  Acid-Treated Metal Oxides .......................... 70
     3.3.5  Heteropoly Acids (HPAs) ............................ 71
     3.3.6  Nation ............................................. 72
     3.3.7  Miscellaneous ...................................... 73
3.4  Direct Phenol Acylation ................................... 73
3.5  Summary and Outlook ....................................... 77
     Abbreviations ............................................. 78
     References ................................................ 78

4    The Use of Quantum Chemistry for Mechanistic Analyses
     of SEAr Reactions ......................................... 83
     Tore Brinck and Magnus Liljenberg
4.1  Introduction .............................................. 83
     4.1.1  Historical Overview of Early Quantum Chemistry
            Work ............................................... 83
     4.1.2  Current Mechanistic Understanding Based on
            Kinetic and Spectroscopic Studies .................. 85
4.2  The SHAr Mechanism: Quantum Chemical Characterization in
     Gas Phase and Solution .................................... 87
     4.2.1  Nitration and Nitrosation .......................... 87
     4.2.2  Halogenation ....................................... 93
     4.2.3  Sulfonation ........................................ 96
     4.2.4  Friedel-Crafts Alkylations and Acylations .......... 96
4.3  Prediction of Relative Reactivity and Regioselectivity
     Based on Quantum Chemical Descriptors ..................... 97
4.4  Quantum Chemical Reactivity Prediction Based on Modeling
     of Transition States and Intermediates ................... 100
     4.4.1  Transition State Modeling ......................... 100
     4.4.2  The Reaction Intermediate or Sigma-Complex
            Approach .......................................... 101
4.5  Summary and Conclusions .................................. 102
Abbreviations ................................................. 103
References .................................................... 103

5    Catalytic Enantioselective Electrophilic Aromatic
     Substitutions ............................................ 107
     Marco Bandini
5.1  Introduction and Historical Background ................... 107
5.2  Metal-Catalyzed AFCA of Aromatic Hydrocarbons ............ 109
     5.2.1  Introduction ...................................... 109
     5.2.2  Metal-Catalyzed Condensation of Arenes with
            Carbonyl Compounds and Their Nitrogen
            Derivatives ....................................... 110
5.3  Organocatalyzed AFCA of Aromatic Hydrocarbons ............ 116
     5.3.1  Introduction ...................................... 116
     5.3.2  Asymmetric Organocatalyzed Condensation of
            Arenes with Carbonyl Compounds and Their
            Nitrogen Derivatives .............................. 117
     5.3.3  Asymmetric Organocatalyzed Alkylations of Arenes
            via Michael Additions ............................. 118
     5.3.4  Organo-SOMO-Catalyzed Asymmetric Alkylations of
            Arenes ............................................ 122
     5.3.5  Miscellaneous in Asymmetric Organocatalyzed
            Alkylations of Arenes ............................. 124
5.4  Merging Asymmetric Metal and Organocatalysis in
     Friedel-Crafts Alkylations ............................... 125
5.5  Summary and Outlook ...................................... 126
     Abbreviations ............................................ 127
     References ............................................... 127

PART II  NUCLEOPHILIC AROMATIC SUBSTITUTION ................... 131

6    Nucleophilic Aromatic Substitution: An Update Overview ... 133
     Michael R. Crampton
6.1  Introduction ............................................. 133
6.2  The S Ar Mechanism ....................................... 135
     6.2.1  Effects of Activating Groups ...................... 138
     6.2.2  Leaving Group Effects ............................. 140
     6.2.3  The Attacking Nucleophile ......................... 141
     6.2.4  Solvent Effects ................................... 145
     6.2.5  Intramolecular Rearrangements ..................... 146
6.3  Meisenheimer Adducts ..................................... 150
     6.3.1  Spectroscopic and Crystallographic Studies ........ 150
     6.3.2  Range and Variety of Substrates and Nucleophiles .. 153
     6.3.3  Superelectrophilic Systems ........................ 158
6.4  The SN1 Mechanism ........................................ 159
     6.4.1  Heterolytic and Homolytic Pathways ................ 159
6.5  Synthetic Applications ................................... 160
     Abbreviations ............................................ 167
     References ............................................... 167

7    Theoretical and Experimental Methods for the Analysis
     of Reaction Mechanisms in SNAr Processes: Fugality
     Philicity and Solvent Effects
     Renato Contreras, Paola R. Campodónico and Rodrigo
     Ormazábal-Toledo
7.1  Introduction ............................................. 175
7.2  Conceptual DFT: Global Regional and Nonlocal Reactivity
     Indices .................................................. 176
7.3  Practical Applications of Conceptual DFT Descriptors ..... 179
     7.3.1  Nucleophilicity and LG Scales ..................... 180
     7.3.2  Activation Properties: Reactivity Indices
            Profiles .......................................... 181
7.4  SNAr Reaction Mechanism .................................. 183
     7.4.1  Kinetic Measurements .............................. 183
     7.4.2  Nucleophilicity LG and PG Abilities ............... 185
7.5  Integrated Experimental and Theoretical Models ........... 187
     7.5.1  Hydrogen Bonding Effects .......................... 187
7.6  Solvent Effects in Conventional Solvents and Ionic
     Liquids .................................................. 188
     7.6.1  Preferential Solvation ............................ 188
     7.6.2  Ionic Liquids and Catalysis ....................... 189
7.7  Summary and Outlook ...................................... 189
     Abbreviations ............................................ 190
     References ............................................... 190

8    Asymmetric Nucleophilic Aromatic Substitution
     Anne-Sophie Castanet, Anne Boussonnière and Jacques
     Mortier
8.1  Introduction ............................................. 195
8.2  Auxiliary- and Substrate-Controlled Asymmetric
     Nucleophilic Aromatic Substitution ....................... 198
     8.2.1  Chiral Electron-Withdrawing Groups ................ 198
     8.2.2  Chiral Leaving Groups ............................. 202
     8.2.3  Planar Chiral Arenes .............................. 205
     8.2.4  Chiral Tethered Arenes ............................ 207
     8.2.5  Chiral Nucleophiles ............................... 209
8.3  Chiral Catalyzed Asymmetric Nucleophilic Aromatic
     Substitution ............................................. 210
     8.3.1  Chiral Ligands .................................... 211
     8.3.2  Chiral Phase Transfer Catalysts ................... 211
8.4  Absolute Asymmetric Nucleophilic Aromatic Substitution ... 213
8.5  Summary and Outlook ...................................... 214
     Abbreviations ............................................ 214
     References ............................................... 215

9    Hemolytic Aromatic Substitution
     Roberto A. Rossi, María E. Budén and Javier F. Guastavino
9.1  Introduction: Scope and Limitations ...................... 219
9.2  Radicals Generated by Homolytic Cleavage Processes:
     Thermolysis and Photolysis ............................... 223
9.3  Reactions Mediated by Tin and Silicon Hydrides ........... 225
9.4  Radicals Generated by ET: Redox Reactions ................ 229
     9.4.1  Reducing Metals ................................... 229
     9.4.2  Other Reducing Agents ............................. 232
     9.4.3  Oxidizing Metals .................................. 233
     9.4.4  Base-Promoted Homolytic Aromatic Substitution
            (BHAS) ............................................ 236
9.5  Summary and Outlook ...................................... 237
     Abbreviations ............................................ 238
     References ............................................... 238

10   Radical-Nucleophilic Aromatic Substitution ............... 243
     Roberto A. Rossi, Javier F. Guastavino and María E. Budén
10.1 Introduction: Scope and Limitations-Background ........... 243
10.2 Mechanistic Considerations ............................... 245
     10.2.1 Initiation Step ................................... 245
     10.2.2 Propagation Steps ................................. 246
     10.2.3 Termination Steps ................................. 248
10.3 Intermolecular SRN1 Reactions ............................ 248
     10.3.1 Nucleophiles from Group 14: С and Sn .............. 248
     10.3.2 Nucleophiles Derived from Group 15: N, P, As and
            Sb ................................................ 254
     10.3.3 Nucleophiles Derived from Group 16: O, S, Se and
            Те ................................................ 256
10.4 Intramolecular SRNl Reactions ............................ 258
10.5 Miscellaneous Ring Closure Reactions ..................... 262
     10.5.1 Exo or Endo Radical Cyclization Followed by an
            SRN1 Reaction ..................................... 262
     10.5.2 Intermolecular SRN1 Reaction Followed by
            Intramolecular SRNl or BHAS Reaction .............. 263
10.6 Summary and Outlook ...................................... 264
     Abbreviations ............................................ 265
     References ............................................... 265

11   Nucleophilic Substitution of Hydrogen in Electron-
     Deficient Arenes ......................................... 269
     Mieczysław Mąkosza
11.1 Introduction ............................................. 269
11.2 Oxidative Nucleophilic Substitution of Hydrogen .......... 270
11.3 Conversion of the aH-Adducts of Nucleophiles to
     Nitroarenes into Substituted Nitrosoarenes ............... 276
11.4 Vicarious Nucleophilic Substitution of Hydrogen .......... 278
     11.4.1 Introduction ...................................... 278
     11.4.2 Mechanism of VNS Reaction ......................... 279
     11.4.3 Scope and Limitation of VNS ....................... 283
11.5 Other Ways of Conversion of the o-H-Adducts .............. 291
11.6 Concluding Remarks ....................................... 293
     Abbreviations ............................................ 295
     References ............................................... 295

PART III ARYNE CHEMISTRY ...................................... 299

12   The Chemistry of Arynes: An Overview ..................... 301
     Roberto Sanz and Anisley Suárez
12.1 Introduction ............................................. 301
12.2 Structure and Representative Reactions of Arynes ......... 301
12.3 Aryne Generation ......................................... 303
     12.3.1 Elimination Methods ............................... 303
     12.3.2 By Hexadehydro-Diels-Alder Reaction ............... 306
     12.3.1 12.4 Pericyclic Reactions ......................... 306
     12.4.1 Diels-Alder Cycloadditions ........................ 306
     12.4.2 [3+2] Cycloadditions .............................. 309
     12.4.3 [2+2] Cycloadditions with Alkenes ................. 311
     12.4.4 Ene Reactions ..................................... 313
12.5 Nucleophilic Addition Reactions to Arynes ................ 314
     12.5.1 Regioselectivity Issues for Functionalized
            Arynes ............................................ 314
     12.5.2 Proton Abstraction: Monosubstitution of the Aryne . 315
     12.5.3 Three-Component Reactions ......................... 317
     12.5.4 Aryne Insertion Reactions into σ-Bonds ............ 321
     12.5.5 Aryne Annulation .................................. 325
12.6 Transition Metal-Catalyzed Reactions of Arynes ........... 327
     12.6.1 Cyclotrimerization of Arynes ...................... 327
     12.6.2 Cocyclization of Arynes with Alkynes .............. 327
     12.6.3 Cocyclization of Arynes with Alkenes .............. 327
     12.6.4 Cocyclization of Arynes Alkenes and Alkynes ....... 329
     12.6.5 Intermolecular Carbopalladation of Arynes ......... 329
     12.6.6 Catalytic Insertion Reactions of Arynes into
            σ-Bonds ........................................... 330
12.7 Conclusion ............................................... 332
Abbreviations ................................................. 332
References .................................................... 333

PART IV  REDUCTION OXIDATION AND DEAROMATIZATION REACTIONS

13   Reduction/Hydrogenation of Aromatic Rings ................ 339
     Francisco Foubelo and Miguel Yus
13.1 Introduction ............................................. 339
13.2 The Birch Reaction ....................................... 339
     13.2.1 Dissolving Metals ................................. 340
     13.2.2 Enzymatic Reactions ............................... 344
13.3 Metal-Catalyzed Hydrogenations ........................... 345
     13.3.1 Homogeneous Conditions ............................ 345
     13.3.2 Heterogeneous Conditions .......................... 351
13.4 Electrochemical Reductions ............................... 357
13.5 Other Methodologies ...................................... 359
13.6 Summary and Outlook ...................................... 361
     Abbreviations ............................................ 361
     References ............................................... 362

14   Selective Oxidation of Aromatic Rings .................... 365
     Oxana A. Kholdeeva
14.1 Introduction ............................................. 365
14.2 Mechanistic Principles ................................... 367
     14.2.1 Autoxidation ...................................... 367
     14.2.2 Spin-Forbidden Reactions with Triplet Oxygen ...... 369
     14.2.3 Radical Hydroxylation (Addition-Elimination) ...... 370
     14.2.4 Electron Transfer Mechanisms ...................... 371
     14.2.5 Electrophilic Hydroxylation via Oxygen Atom
            Transfer .......................................... 373
     14.2.6 Heterolytic Activation of Substrate ............... 374
14.3 Stoichiometric Oxidations ................................ 374
14.4 Catalytic Oxidations ..................................... 375
     14.4.1 Benzene ........................................... 375
     14.4.2 Polycyclic Arenes ................................. 379
     14.4.3 Alkylarenes ....................................... 379
     14.4.4 Electron-Poor Aromatic Compounds .................. 382
     14.4.5 ortho-Hydroxylation Driven by Arene Functional
            Group ............................................. 382
     14.4.6 Phenol ............................................ 383
     14.4.7 Alkylphenols and Alkoxyarenes ..................... 384
14.5 Photochemical Oxidations ................................. 386
14.6 Electrochemical Oxidations ............................... 387
14.7 Enzymatic Hydroxylation .................................. 389
14.8 Summary and Outlook ...................................... 390
     Acknowledgments .......................................... 391
     Abbreviations ............................................ 391
     References ............................................... 392

15   Dearomatization Reactions: An Overview ................... 399
     F. Christopher Pigge
15.1 Introduction ............................................. 399
15.2 Alkylative Dearomatization ............................... 400
     15.2.1 C-Alkylation of Phenolate Anions .................. 400
     15.2.2 Anionic Dearomatization ........................... 401
     15.2.3 Radical Dearomatization ........................... 403
15.3 Photochemical and Thermal Dearomatization ................ 405
     15.3.1 Dearomatization by Photocycloaddition ............. 405
     15.3.2 Dearomatization by Thermally Induced
            Rearrangement ..................................... 406
15.4 Oxidative Dearomatization ................................ 408
     15.4.1 Oxidative Dearomatization with Formation of
            Carbon-Heteroatom Bonds ........................... 408
     15.4.2 Oxidative Dearomatization with Formation of
            Carbon-Carbon Bonds ............................... 411
15.5 Transition Metal-Assisted Dearomatization ................ 413
     15.5.1 Dearomatization Reactions of Metal Carbenoids ..... 413
     15.5.2 Dearomatization Catalyzed by Palladium
            Iridium and Related Complexes ..................... 413
     15.5.3 Dearomatization of n2-Arene Metal Complexes ....... 416
     15.5.4 Dearomatization of n6-Arene Metal Complexes ....... 417
15.6 Enzymatic Dearomatization ................................ 418
15.7 Conclusions and Future Directions ........................ 419
     Abbreviations ............................................ 419
     References ............................................... 420

PART V AROMATIC REARRANGEMENTS ................................ 425

16   Aromatic Compounds via Pericyclic Reactions .............. 427
     Sethuraman Sankararaman
16.1 Introduction ............................................. 427
16.2 Electrocyclic Ring Closure Reaction ...................... 428
     16.2.1 Application of Electrocyclic Ring Closure in
            Aromatic Synthesis ................................ 429
16.3 Introduction to Cycloaddition Reactions .................. 433
     16.3.1 Application of [4+2] Cycloaddition Method for
            Synthesis of Aromatic Compounds ................... 434
16.4 Conclusions .............................................. 448
     Abbreviations ............................................ 448
     References ............................................... 448

17   Ring-Closing Metathesis: Synthetic Routes to
     Carbocyclic Aromatic Compounds using Ring-Closing
     Alkene and Enyne Metathesis .............................. 451
     Charles B. de Koning and Willem A.L. van Otterlo
17.1 Introduction ............................................. 451
17.2 Alkene RCM for the Synthesis of Aromatic Compounds ....... 454
     17.2.1 Synthesis of Substituted Benzenes ................. 454
     17.2.2 Synthesis of Substituted Naphthalenes ............. 458
     17.2.3 Synthesis of Substituted Phenanthrenes ............ 458
     17.2.4 Synthesis of Anthraquinones and Benzo-Fused
            Anthraquinones .................................... 459
     17.2.5 Applications in the Synthesis of Polyarenes ....... 461
     17.2.6 Applications in the Synthesis of Natural
            Products .......................................... 462
17.3 Enyne Metathesis Followed by the Diels-Alder Reaction
     for the Synthesis of Benzene Rings in Complex Aromatic
     Compounds ................................................ 464
     17.3.1 Synthesis of Substituted Benzenes ................. 464
     17.3.2 Synthesis of Substituted Phenanthrenes ............ 466
     17.3.3 Synthesis of Complex Naphthoquinones and
            Anthraquinones .................................... 466
     17.3.4 Applications to the Synthesis of Biologically
            Active Products ................................... 470
17.4 Cyclotrimerization for the Synthesis of Aromatic
     Compounds by Metathetic Processes ........................ 470
17.5 Strategies for the Synthesis of Aromatic Carbocycles
     Fused to Heterocycles by the RCM Reaction ................ 472
     17.5.1 Alkene RCM for the Synthesis of Benzene Rings in
            Indoles Carbazoles Benzo-Fused Pyridines and
            Pyridones and Benzo-Fused Imidazoles .............. 472
     17.5.2 Enyne RCM for the Synthesis of Benzene Rings in
            Tetrahydroisoquinolines Annulated 1,2-Oxaza- and
            1,2-Bisazacycles and Indoles ...................... 479
17.6 Future Challenges ........................................ 481
17.7 Conclusions .............................................. 481
     Abbreviations ............................................ 482
     References ............................................... 482

18   Aromatic Rearrangements in which the Migrating Group
     Migrates to the Aromatic Nucleus: An Overview ............ 485
     Timothy J. Snape
18.1 Introduction ............................................. 485
18.2 Mechanisms by Classification ............................. 486
     18.2.1 Intramolecular Reactions: Nucleophilic Aromatic
            Substitution ...................................... 486
     18.2.2 Intramolecular: Sigmatropic Rearrangements ........ 494
     18.2.3 Intermolecular Rearrangements ..................... 500
18.3 Summary and Outlook ...................................... 508
     Abbreviations ............................................ 508
     References ............................................... 508

PART VI. TRANSITION METAL-MEDIATED COUPLING ................... 511

19   Transition Metal-Catalyzed Carbon-Carbon Cross-Coupling .. 513
     Anny Jutand and Guillaume Lefèvre
19.1 Introduction ............................................. 513
19.2 The Mizoroki-Heck Reaction ............................... 513
     19.2.1 General Considerations and Mechanisms ............. 513
     19.2.2 Scope of the Reaction ............................. 520
     19.2.3 Synthetic Application ............................. 523
19.3 Cross-Coupling of Aryl Halides with Anionic
     C-Nucleophiles ........................................... 523
     19.3.1 The Kumada Reactions: Nickel-Catalyzed Cross-
            Coupling with Grignard Reagents ................... 523
     19.3.2 Palladium-Catalyzed Cross-Coupling with Grignard
            Reagents .......................................... 524
     19.3.3 The Negishi Reaction: Palladium-Catalyzed Cross-
            Coupling with Organozinc Reagents ................. 525
     19.3.4 Palladium-Catalyzed Cross-Coupling with
            Organolithium Reagents ............................ 525
     19.3.5 Mechanism of Palladium-Catalyzed Cross-Couplings
            with Rm (m=Li,MgY,ZnY) ............................ 526
     19.3.6 Nickel- and Palladium-Catalyzed Arylation of
            Ketone Ester and Amide Enolates ................... 528
19.4 The Sonogashira Reaction ................................. 530
     19.4.1 General Considerations and Mechanism .............. 530
     19.4.2 Synthetic Applications ............................ 531
19.5 The Stille Reaction ...................................... 532
     19.5.1 General Considerations and Mechanism .............. 532
     19.5.2 Synthetic Application ............................. 533
19.6 The Suzuki-Miyaura Reaction .............................. 534
     19.6.1 General Considerations and Mechanism .............. 534
     19.6.2 Synthetic Application ............................. 539
19.7 The Hiyama Reaction ...................................... 539
     19.7.1 General Considerations and Mechanism .............. 539
     19.7.2 Synthetic Applications ............................ 541
19.8 Summary and Outlook ...................................... 541
     Abbreviations ............................................ 541
     References ............................................... 541

20   Transition Metal-Mediated Carbon-Heteroatom Cross-
     Coupling (C-N, C-O, C-S, C-Se, C-Te, C-P, C-As, C-Sb and
     C-B Bond Forming Reactions): An Overview ................. 547
     Masanam Kannan, Mani Sengoden and Tharmalingam
     Punniyamurthy
20.1 Introduction ............................................. 547
20.2 C-N Cross-Coupling ....................................... 550
     20.2.1 Palladium-Catalyzed Reactions ..................... 550
     20.2.2 Copper-Catalyzed Reactions ........................ 555
     20.2.3 Other Transition Metal-Catalyzed Reactions ........ 559
     20.2.4 Synthetic Applications ............................ 560
20.3 С-О Cross-Coupling ....................................... 561
     20.3.1 Reactions with Aromatic Alcohols .................. 561
     20.3.2 Reactions with Aliphatic Alcohols ................. 563
     20.3.3 Synthesis of Phenols .............................. 566
     20.3.4 Synthetic Applications ............................ 567
20.4 С-S Cross-Coupling ....................................... 569
     20.4.1 Palladium-Catalyzed Reactions ..................... 569
     20.4.2 Copper-Catalyzed Reactions ........................ 569
     20.4.3 Other Transition Metal-Catalyzed Reactions ........ 570
20.5 C-Se Cross-Coupling ...................................... 571
20.6 С-Те Cross-Coupling ...................................... 571
20.7 C-P Cross-Coupling ....................................... 572
     20.7.1 Palladium-Catalyzed Reactions ..................... 572
     20.7.2 Copper-Catalyzed Reactions ........................ 576
     20.7.3 Nickel-Catalyzed Reactions ........................ 577
20.8 C-As and C-Sb Cross-Coupling ............................. 578
20.9 С-В Cross-Coupling ....................................... 578
20.10 Summary and Outlook ..................................... 579
     Abbreviations ............................................ 579
     References ............................................... 579

21   Transition Metal-Mediated Aromatic Ring Construction
     Ken Tanaka
21.1 Introduction ............................................. 587
21.2 [2+2+2] Cycloaddition .................................... 587
     21.2.1 Mechanism ......................................... 588
     21.2.2 [2+2+2] Cycloaddition of Monoynes ................. 589
     21.2.3 [2+2+2] Cycloaddition of Diynes with Monoynes ..... 590
     21.2.4 [2+2+2] Cycloaddition of Triynes .................. 598
21.3 [3+2+1] Cycloaddition .................................... 601
21.4 [4+2] Cycloaddition ...................................... 602
     21.4.1 Diels-Alder Reactions ............................. 602
     21.4.2 Reactions of Enynes with Alkynes .................. 603
     21.4.3 Reactions via Pyrylium Intermediates .............. 606
     21.4.4 Reactions via АсуImetallacycles ................... 607
21.5 Intramolecular Cycloaromatization ........................ 608
     21.5.1 Intramolecular Hydroarylation of Alkynes .......... 608
     21.5.2 Cyclization via Transition Metal Vinylidenes ...... 610
21.6 Summary and Outlook ...................................... 612
     References ............................................... 612

22   Ar-C Bond Formation by Aromatic Carbon-Carbon
     ipso-Substitution Reaction
     Maurizio Fagnoni and Sergio M. Bonesi
22.1 Introduction ............................................. 615
22.2 Formation of Ar-C(sp3) Bonds ............................. 616
     22.2.1 Ni-Catalyzed Reactions ............................ 616
     22.2.2 Rh-Catalyzed Reactions ............................ 617
     22.2.3 Pd-Catalyzed Reactions ............................ 619
22.3 Formation of Ar-C(sp2) Bonds ............................. 620
     22.3.1 Synthesis of Aryl Ketones and Amidines ............ 620
     22.3.2 Formation of Ar-Vinyl Bonds ....................... 620
     22.3.3 Formation of Ar-Ar Bonds .......................... 628
     22.3.4 Formation of Benzocondensed Derivatives ........... 636
     22.3.1 Formation of Ar-C(sp) Bonds ....................... 638
22.5 Summary and Outlook ...................................... 639
     Abbreviations ............................................ 639
     References ............................................... 640

PART VII  С-H FUNCTIONALIZATION ............................... 645

23   Chelate-Assisted Arene C-H Bond Functionalization ........ 647
     Marion H. Emmert and Christopher J. Legacy
23.1 Introduction ............................................. 647
     23.1.1 Mechanisms of Chelate-Assisted C-H Bond
            Functionalization and Activation .................. 648
     23.1.2 Weakly and Strongly Coordinating Directing
            Groups ............................................ 651
     23.1.3 Common Directing Groups ........................... 651
     23.1.4 Transformable and In Situ Generated Directing
            Groups ............................................ 652
23.2 Carbon-Carbon (C-C) Bond Formations ...................... 654
     23.2.1 C-CAryl Bond Formations ............................ 654
     23.2.2 C-CAlkenyl Bond Formations .......................... 655
     23.2.3 C-CAlkyl Bond Formations ........................... 656
     23.2.4 C-CAcyl Bond Formations ............................ 657
     23.2.5 C-CN Bond Formations .............................. 658
     23.2.6 C-CF3 Bond Formations ............................. 659
23.3 Carbon-Heteroatom (C-X) Bond Formations .................. 660
     23.3.1 C-B Bond Formations ............................... 660
     23.3.2 C-Si Bond Formations .............................. 661
     23.3.3 C-O Bond Formations ............................... 662
     23.3.4 C-N Bond Formations ............................... 662
     23.3.5 C-P Bond Formations ............................... 664
     23.3.6 C-S Bond Formations ............................... 665
     23.3.7 C-Halogen Bond Formations ......................... 666
     23.3.8 C-D Bond Formations ............................... 667
23.4 Stereoselective C-H Functionalizations ................... 668
     Abbreviations ............................................ 669
     References ............................................... 669

24   Reactivity and Selectivity in Transition Metal-Catalyzed,
     Nondirected Arene Functionalizations ..................... 675
     Dipannita Kalyani and Elodie E. Marlier
24.1 Introduction ............................................. 675
24.2 Arylation ................................................ 676
     24.2.1 Direct Arylations ................................. 677
     24.2.2 Cross-Dehydrogenative Arylations .................. 684
24.3 Alkenylatjon ............................................. 693
24.4 Alkylation ............................................... 699
24.5 Carboxylation ............................................ 701
24.6 Oxygenation .............................................. 701
24.7 Thiolation ............................................... 704
24.8 Animation ................................................ 706
24.9 Miscellaneous ............................................ 708
     24.9.1 Halogenation ...................................... 708
     24.9.2 Silylation ........................................ 708
     24.9.3 Borylation ........................................ 709
24.10 Summary and Outlook ..................................... 710
     Abbreviations ............................................ 710
     References ............................................... 710

25   Functionalization of Arenes via С-H Bond Activation
     Catalysed by Transition Metal Complexes: Synergy
     between Experiment and Theory ............................ 715
     Amalia Isabel Poblador-Bahamonde
25.1 Introduction ............................................. 715
25.2 Mechanisms of C-H Bond Activation ........................ 716
25.3 Development of Stoichiometric C-H Bond Activation ........ 718
     25.3.1 Mechanistic Ambiguity: The Power of Theory ........ 721
     25.3.2 C-H Activation Assisted by Carboxylate or
            Carbonate Bases ................................... 723
25.4 Catalytic C-H Activation and Functionalization ........... 730
     25.4.1 Hydroarylation of Alkenes ......................... 730
     25.4.2 Arene Functionalization via a Base-Assisted
            Mechanism ......................................... 735
25.5 Summary .................................................. 738
     Abbreviations ............................................ 738
     References ............................................... 738

PART VIII. DIRECTED METALATION REACTIONS ...................... 741

26   Directed Metalation of Arenes with Organolithiums
     Lithium Amides, and Superbases ........................... 743
     Frédéric R. Leroux and Jacques Mortier
26.1 Introduction ............................................. 743
26.2 Preparation and Reactivity of Organolithium Compounds .... 744
     26.2.1 Bases and Complexing Agents ....................... 744
     26.2.2 Solvents .......................................... 746
     26.2.3 Electrophiles ..................................... 747
26.3 Directed or//io-Metalation (DoM) ......................... 748
     26.3.1 Mechanisms: Complex-Induced Proximity Effect
            Process Kinetically Enhanced Metalation and
            Overriding Base Mechanism ......................... 748
     26.3.2 Directing Metalation Groups (DMGs) ................ 750
     26.3.3 Optional Site Selectivity: Selected Examples ...... 750
     26.3.4 External and In Situ Quench Conditions ............ 754
     26.3.5 Apparent Anomalies in the Reactivity of Certain
            Electrophiles ..................................... 756
26.4 Directed remote Metalation (DreM) ........................ 757
26.5 Peri Lithiation of Substituted Naphthalenes .............. 759
26.6 Lithiation of Metal Arene Complexes ...................... 760
26.7 Lateral Lithiation ....................................... 761
26.8 Analytical Methods ....................................... 762
     26.8.1 Quantitative Determination of Organolithiums ...... 762
     26.8.2 Qualitative Determination of Organolithiums ....... 763
     26.8.3 Crystallography ................................... 763
     26.8.4 NMR Spectroscopy .................................. 765
26.9 Synthetic Applications ................................... 765
     26.9.1 DoM and С-С Cross-Coupling ........................ 765
     26.9.2 DoM, DreM, and Anionic Fries Rearrangement ........ 766
     26.9.3 Industrial Scale-Up of Ortho Metalation
            Reactions ......................................... 768
     26.9.4 Lateral Lithiation ................................ 768
     26.9.5 Superbase Metalation .............................. 769
26.10 Conclusion .............................................. 770
     Abbreviations ............................................ 771
     References ............................................... 771

27   Deprotonative Metalation Using Alkali Metal-Nonalkali
     Metal Combinations ....................................... 777
     Floris Chevallier, Florence Mongin, Ryo Takita and
     Masanobu Uchiyama
27.1 Introduction ............................................. 777
27.2 Preparation of the Bimetallic Combinations and their
     Structural Features ...................................... 778
     27.2.1 Preparation of Alkali Metal-Nonalkali Metal
            Basic Combinations ................................ 778
     27.2.2 Ate Compounds ..................................... 778
     27.2.3 Salt-Activated Compounds .......................... 779
     27.2.4 Contacted and Solvent-Separated Ion Pairs ......... 779
27.3 Behavior of Alkali Metal-Nonalkali Metal Combinations .... 779
     27.3.1 One-Electron and Two-Electron Transfers ........... 779
     27.3.2 Base and Nucleophile Ligand Transfers ............. 780
27.4 Mechanistic Studies on the Deprotometalation Using
     Alkali Metal-Nonalkali Metal Combinations ................ 780
     27.4.1 Deprotometalation Using Alkali Metal-
            Amidozincate Complexes ............................ 780
     27.4.2 Deprotometalation Using Alkali Metal-
            Amidoaluminate Complexes .......................... 783
     27.4.3 Deprotometalation Using Alkali Metal-
            Amidocuprate Complexes ............................ 786
     27.4.4 Deprotometalation Using Alkali Metal-Amidocadmate
            Complexes ......................................... 789
27.5 Scope and Applications of the Deprotometalation .......... 790
     27.5.1 Using Lithium- or Sodium-Magnesium Mixed-Metal
            Bases ............................................. 790
     27.5.2 Using Lithium-Aluminum Mixed-Metal Bases .......... 793
     27.5.3 Using Lithium-, Sodium- or Magnesium-Manganese
            Mixed-Metal Bases ................................. 795
     27.5.4 Using Lithium- Sodium- or Magnesium-Iron Mixed-
            Metal Bases ....................................... 798
     27.5.5 Using Lithium-Cobalt Mixed-Metal Bases ............ 799
     27.5.6 Using Lithium-Copper Mixed-Metal Bases ............ 799
     27.5.7 Using Lithium-Sodium- or Magnesium-Zinc
            Mixed-Metal Bases ................................. 799
     27.5.8 Using Lithium- or Magnesium-Zirconium Mixed-Metal
            Bases ............................................. 804
     27.5.9 Using Lithium-Cadmium Mixed-Metal Bases ........... 804
     27.5.10 Using Lithium-or Magnesium-Lanthanum Mixed-
            Metal Bases ....................................... 805
27.6 Conclusion and Perspectives .............................. 807
     Acknowledgments .......................................... 807
     Abbreviations ............................................ 807
     References ............................................... 811

28   The Halogen/Metal Interconversion and Related
     Processes (M=Li, Mg) ..................................... 813
     Armen Panossian and Frederic R. Leroux
28.1 Introduction ............................................. 813
28.2 Generalities ............................................. 814
     28.2.1 Monometallic Organolithium Reagents ............... 814
     28.2.2 Monometallic Organomagnesium Reagents ............. 814
     28.2.3 Bimetallic Organolithium/Magnesium Reagents ....... 814
     28.3 Mechanism of the Halogen/Metal Interconversion ...... 815
     28.3.1 Reactivity ........................................ 815
     28.3.2 Mechanism ......................................... 816
28.4 Halogen Migration on Aromatic Compounds .................. 817
28.5 Selective Synthesis via Halogen/Metal Interconversion .... 818
     28.5.1 Chemo and Regioselectivity of Halogen/Metal
            Interconversions .................................. 818
     28.5.2 Stereoselectivity of Halogen/Metal
            Interconversions .................................. 821
28.6 The Sulfoxide/Metal and Phosphorus/Metal
     Interconversions ......................................... 822
     28.6.1 The Sulfoxide/Metal Interconversion ............... 822
     28.6.2 The Phosphorus/Metal Interconversion .............. 826
28.7 Aryl-Aryl Coupling Through Halogen/Metal
     Interconversion .......................................... 827
     28.7.1 (Re)emerging Methods for Aryl-Aryl Coupling
            Through Halogen/Metal Interconversion ............. 827
     28.7.2 Aryne-Mediated Aryl-Aryl Coupling ................. 828
28.8 Summary and Outlook ...................................... 830
     Abbreviations ............................................ 830
     References ............................................... 830

PART IX  PHOTOCHEMICAL REACTIONS

29   Aromatic Photochemical Reactions
     Norbert Hoffmann and Emmanuel Riguet
29.1 Introduction ............................................. 837
29.2 Aromatic Compounds as Chromophores ....................... 838
     29.2.1 Photocycloaddition and Photochemical
            Electrocyclic Reactions Involving Aromatics ....... 838
     29.2.2 Photoinduced Radical Reactions .................... 842
29.3 Photosensitized and Photocatalyzed Reactions ............. 849
     29.3.1 Metal-Catalyzed Reactions ......................... 849
     29.3.2 Metal-Free Reactions .............................. 856
29.4 Conclusion ............................................... 864
     Abbreviation ............................................. 865
     References ............................................... 865

30   Photochemical Bergman Cyclization and Related Reactions
     Rana К. Mohamed, Kemal Kaya and Igor V. Alabugin
30.1 Introduction: The Diversity of Cycloaromatization
     Reactions ................................................ 869
30.2 Electronic Factors in Photo-BC ........................... 870
     30.2.1 Substituent Effects ............................... 872
     30.2.2 Introducing Strain ................................ 872
     30.3 Scope and Limitations of the Photo-BC ............... 876
     30.3.1 Metal-Mediated Photochemistry ..................... 876
     30.3.2 Diverting from ВС Pathway: Direct Excitation
            and Photoinduced Electron Transfer ................ 881
30.4 Enediyne Photocyclizations: Tool for Cancer Therapy ...... 883
30.5 Conclusion ............................................... 883
     Abbreviations ............................................ 885
     References ............................................... 885

31   Photo-Fries Reaction and Related Processes ............... 889
     Francisco Galindo, M. Consuelo Jimenez  and Miguel
     Angel Miranda
31.1 Introduction ............................................. 889
31.2 Mechanistic Aspects ...................................... 889
     31.2.1 General Scheme .................................... 889
     31.2.2 Experimental Evidence: Steady-State Photolysis .... 890
     31.2.3 Experimental Evidence: Time-Resolved Studies ...... 891
     31.2.4 Experimental Evidence: Spin Chemistry Techniques .. 894
     31.2.5 Theoretical Studies ............................... 894
31.3 Scope of the Reaction .................................... 894
     31.3.1 Esters ............................................ 894
     31.3.2 Amides ............................................ 895
     31.3.3 Other ............................................. 895
31.4 (Micro)Heterogeneous Systems as Reaction Media ........... 897
     31.4.1 Cyclodextrins ..................................... 897
     31.4.2 Micelles .......................................... 897
     31.4.3 Zeolites .......................................... 897
     31.4.4 Proteins .......................................... 897
     31.4.5 Other Organized Media ............................. 897
31.5 Applications in Organic Synthesis ........................ 900
31.6 Biological and Industrial Applications ................... 902
     31.6.1 Drugs ............................................. 902
     31.6.2 Agrochemicals ..................................... 902
     31.6.3 Polymers .......................................... 904
31.7 Summary and Outlook ...................................... 905
     Abbreviations ............................................ 906
     References ............................................... 906

PART X BIOTRANSFORMATIONS ..................................... 913

32   Biotransformations of Arenes: An Overview ................ 915
     Simon E. Lewis
32.1 Introduction ............................................. 915
32.2 Dearomatizing Arene Dihydroxylation ...................... 915
32.3 Dearomatizing Arene Epoxidation .......................... 918
32.4 Arene Alkylation (Biocatalytic Friedel-Crafts) ........... 919
32.5 Arene Deacylation (Biocatalytic Retro Friedel-Crafts) .... 922
32.6 Arene Carboxylation (Biocatalytic Kolbe-Schmitt) ......... 923
32.7 Arene Halogenation (Halogenases) ......................... 925
32.8 Arene Oxidation with Laccases ............................ 925
32.9 Tetrahydroisoquinoline Synthesis (Biocatalytic Pictet-
     Spengler) ................................................ 929
32.10 Arene Hydroxylation ..................................... 930
32.11 Arene Nitration ......................................... 932
32.12 Summary and Outlook ..................................... 933
     Abbreviations ............................................ 934
     References ............................................... 934

INDEX ......................................................... 939

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Посещение N 227 c 14.11.2017