Jacques Mortier

Arene Chemistry

Reaction Mechanisms and Methods for Aromatic Compounds

• Gebundenes Buch

Produktbeschreibung

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

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Produktdetails

• Verlag: John Wiley & Sons / Wiley
• Seitenzahl: 992
• Erscheinungstermin: 14. Dezember 2015
• Englisch
• Abmessung: 240mm x 161mm x 57mm
• Gewicht: 1628g
• ISBN-13: 9781118752012
• ISBN-10: 1118752015
• Artikelnr.: 42648650

Autorenporträt

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).

Inhaltsangabe

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 2.3 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 ipsöFC 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 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 11.5 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 12.4 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 ipsöSubstitution 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 PhotöBC, 870 30.3 Scope and Limitations of the PhotöBC, 876 30.4 Enediyne Photocyclizations: Tool for Cancer Therapy, 883 30.5 Conclusion, 883 Abbreviations, 885 References, 885 31 PhotöFries 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