Arene Chemistry: Reaction Mechanisms and Methods for Aromatic Compounds » książka
Arene Chemistry: Reaction Mechanisms and Methods for Aromatic Compounds
ISBN-13: 9781118752012 / Angielski / Twarda / 2015 / 992 str.
Arene Chemistry: Reaction Mechanisms and Methods for Aromatic Compounds
ISBN-13: 9781118752012 / Angielski / Twarda / 2015 / 992 str.
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Organized to enable students and synthetic chemists to understand and expand on aromatic reactions covered in foundation courses, the book offers a thorough and accessible mechanistic explanation of aromatic reactions involving arene compounds.
- Surveys methods used for preparing arene compounds and their transformations
- Connects reactivity and methodology with mechanism
- Helps readers apply aromatic reactions in a practical context by designing syntheses
- Provides essential information about techniques used to determine reaction mechanisms
Organized to enable students and synthetic chemists to understand and expand on aromatic reactions covered in foundation courses, the book offers a thorough and accessible mechanistic explanation of aromatic reactions involving arene compounds.
LIST OF CONTRIBUTORS xxi
PREFACE xxv
PART I ELECTROPHILIC AROMATIC SUBSTITUTION 1
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 Complex Intermediates, 17
1.6 Complex or Wheland Intermediates, 22
1.7 Summary and Outlook, 27
Abbreviations, 27
References, 28
2 Friedel Crafts Alkylation of Arenes in Total Synthesis 33
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 Q10, 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 C C Bond Formation Leading to Homocyclic Rings, 37
2.3.2 C C Bond Formation Leading to Oxygen Containing Rings, 43
2.3.3 C C Bond Formation Leading to Nitrogen Containing Rings, 44
2.4 Total Synthesis Through Tandem and Cascade Processes Involving FC Reactions, 46
2.4.1 C C Bond Formation Leading to Homocyclic Rings, 46
2.4.2 C C Bond Formation Leading to Oxygen Containing Rings, 49
2.4.3 C C 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 Nafion, 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 SEAr 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 SNAr 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 175
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 195
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 Homolytic Aromatic Substitution 219
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: C 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 Te, 256
10.4 Intramolecular SRN1 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 SRN1 or BHAS Reaction, 263
10.6 Summary and Outlook, 264
Abbreviations, 265
References, 265
11 Nucleophilic Substitution of Hydrogen in Electron Deficient Arenes 269
Mieczys aw M kosza
11.1 Introduction, 269
11.2 Oxidative Nucleophilic Substitution of Hydrogen, 270
11.3 Conversion of the H 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 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
12.4 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 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 Bonds, 330
12.7 Conclusion, 332
Abbreviations, 332
References, 333
PART IV REDUCTION, OXIDATION, AND DEAROMATIZATION REACTIONS 337
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 2 Arene Metal Complexes, 416
15.5.4 Dearomatization of 6 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 C O 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 C 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 C Te 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 C B Cross Coupling, 578
20.10 Summary and Outlook, 579
Abbreviations, 579
References, 579
21 Transition Metal Mediated Aromatic Ring Construction 587
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 Acylmetallacycles, 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 615
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
22.4 Formation of Ar C(sp) Bonds, 638
22.5 Summary and Outlook, 639
Abbreviations, 639
References, 640
PART VII C 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 Alkenylation, 693
24.4 Alkylation, 699
24.5 Carboxylation, 701
24.6 Oxygenation, 701
24.7 Thiolation, 704
24.8 Amination, 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 C 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 ortho–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 C C 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, 807
28 The Halogen/Metal Interconversion and Related Processes (M = Li, Mg) 813
Armen Panossian and Frédéric 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 835
29 Aromatic Photochemical Reactions 837
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 869
Rana K. 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 BC 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 Jiménez, 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
Jacques Mortier, PhD, is Professor of Organic Chemistry at the University of Maine in Le Mans (France), where he teaches classes on Industrial Organic Chemistry and Reaction Mechanisms in Aromatic and Heteroaromatic Chemistry. Dr. Mortier started his career as a research chemist in the crop protection industry. At the University of Maine, his research is focused on various topics dealing with polar organometallics, directed aromatic metalation methodologies, and the study of reaction mechanisms. He has extensive experience as a consultant for the chemical industry. In recognition of his research expertise, he was distinguished as a member of the University Institute of France (IUF).
Arenes, or aromatic compounds, have tremendous importance in industrial chemical applications used across such diverse industries as pharmaceuticals, dyes, and polymers. Given the utility of aromatic reactions, there is real need for a book focusing on mechanisms and strategies for aromatic reactions.
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Arene Chemistry offers a valuable reference and resource for the organic chemistry community. Key benefits include:
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