Arene Chemistry
John Wiley & Sons Inc (Verlag)
978-1-118-75201-2 (ISBN)
• 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
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).
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 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 33
Gonzalo Blay, Marc Montesinos‐Magraner, and José R. Pedro
2.1 Introduction, 33
2.2 Total Synthesis Involving Intermolecular FC Alkylations, 34
2.3 Total Synthesis Involving Intramolecular FC Alkylations, 37
2.4 Total Synthesis Through Tandem and Cascade Processes Involving FC Reactions, 46
2.5 Total Synthesis Involving ipso‐FC Reactions, 54
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
3.3 Catalytic Heterogeneous Acylations, 64
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
4.2 The SEAr Mechanism: Quantum Chemical Characterization in Gas Phase and Solution, 87
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
4.5 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
5.3 Organocatalyzed AFCA of Aromatic Hydrocarbons, 116
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
6.3 Meisenheimer Adducts, 150
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
7.4 SNAr Reaction Mechanism, 183
7.5 Integrated Experimental and Theoretical Models, 187
7.6 Solvent Effects in Conventional Solvents and Ionic Liquids, 188
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
8.3 Chiral Catalyzed Asymmetric Nucleophilic Aromatic Substitution, 210
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
9.5 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
10.3 Intermolecular SRN1 Reactions, 248
10.4 Intramolecular SRN1 Reactions, 258
10.5 Miscellaneous Ring Closure Reactions, 262
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 σH‐Adducts of Nucleophiles to Nitroarenes into Substituted Nitrosoarenes, 276
11.4 Vicarious Nucleophilic Substitution of Hydrogen, 278
11.5 Other Ways of Conversion of the σH‐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
12.4 Pericyclic Reactions, 306
12.5 Nucleophilic Addition Reactions to Arynes, 314
12.6 Transition Metal–Catalyzed Reactions of Arynes, 327
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
13.3 Metal‐Catalyzed Hydrogenations, 345
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
14.3 Stoichiometric Oxidations, 374
14.4 Catalytic Oxidations, 375
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
15.3 Photochemical and Thermal Dearomatization, 405
15.4 Oxidative Dearomatization, 408
15.5 Transition Metal‐Assisted Dearomatization, 413
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
16.3 Introduction to Cycloaddition Reactions, 433
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
17.3 Enyne Metathesis Followed by the Diels–Alder Reaction for the Synthesis of Benzene Rings in Complex Aromatic Compounds, 464
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
17.6 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
18.3 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
19.3 Cross‐Coupling of Aryl Halides with Anionic C‐Nucleophiles, 523
19.4 The Sonogashira Reaction, 530
19.5 The Stille Reaction, 532
19.6 The Suzuki–Miyaura Reaction, 534
19.7 The Hiyama Reaction, 539
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
20.3 C—O Cross‐Coupling, 561
20.4 C—S Cross‐Coupling, 569
20.5 C—Se Cross‐Coupling, 571
20.6 C—Te Cross‐Coupling, 571
20.7 C—P Cross‐Coupling, 572
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
21.3 [3+2+1] Cycloaddition, 601
21.4 [4+2] Cycloaddition, 602
21.5 Intramolecular Cycloaromatization, 608
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
22.3 Formation of Ar–C(sp2) Bonds, 620
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
23.2 Carbon–Carbon (C–C) Bond Formations, 654
23.3 Carbon–Heteroatom (C–X) Bond Formations, 660
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
24.3 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
24.10 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
25.4 Catalytic C─H Activation and Functionalization, 730
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
26.3 Directed ortho-Metalation (DoM), 748
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
26.9 Synthetic Applications, 765
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
27.3 Behavior of Alkali Metal–Nonalkali Metal Combinations, 779
27.4 Mechanistic Studies on the Deprotometalation Using Alkali Metal–Nonalkali Metal Combinations, 780
27.5 Scope and Applications of the Deprotometalation, 790
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
28.3.1 Reactivity, 815
28.2.1 Monometallic Organolithium Reagents, 814
28.3 Mechanism of the Halogen/Metal Interconversion, 815
28.4 Halogen Migration on Aromatic Compounds, 817
28.5 Selective Synthesis via Halogen/Metal Interconversion, 818
28.6 The Sulfoxide/Metal and Phosphorus/Metal Interconversions, 822
28.7 Aryl─Aryl Coupling Through Halogen/Metal Interconversion, 827
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
29.3 Photosensitized and Photocatalyzed Reactions, 849
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
30.3 Scope and Limitations of the Photo‐BC, 876
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
31.3 Scope of the Reaction, 894
31.4 (Micro)Heterogeneous Systems as Reaction Media, 897
31.5 Applications in Organic Synthesis, 900
31.6 Biological and Industrial Applications, 902
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
| Verlagsort | New York |
|---|---|
| Sprache | englisch |
| Maße | 158 x 239 mm |
| Gewicht | 1497 g |
| Themenwelt | Naturwissenschaften ► Chemie ► Organische Chemie |
| ISBN-10 | 1-118-75201-5 / 1118752015 |
| ISBN-13 | 978-1-118-75201-2 / 9781118752012 |
| Zustand | Neuware |
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