Mortier

Arene Chemistry

• 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

Produktdetails

• Verlag: John Wiley & Sons / Wiley
• Seitenzahl: 992
• Erscheinungstermin: 11. 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 pi-Complex Intermediates
17 1.6 sigma-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 6.5 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 MieczysBaw Mkosza 11.1 Introduction
269 11.2 Oxidative Nucleophilic Substitution of Hydrogen
270 11.3 Conversion of the sigmaH-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 sigmaH-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 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