WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2009. - 543 p.
Arenes and heteroarenes are essential substructures of numerous compounds with activities that are relevant to a variety of important areas of research, ranging inter alia from medicinal chemistry and biology to materials sciences. As a result, the selective preparation of these omnipresent moieties is of the utmost relevance to synthetic chemists, both in industry and academia.
Within the book, following a brief introduction, industrial practitioners review important transition metal - catalyzed cross - coupling reactions, as well as carbon – heteroatom bond - forming processes. The infl uence of catalytic strategies – and particularly of those that employ transition metal complexes – on arylation reactions with haloalkanes, alkenes, alkynes and carbonyl compounds as substrates is subsequently described. The next three chapters detail not only the experimental observations but also the mechanistic considerations of ecologically benign C – H bond functionalization reactions. Finally, the book concludes with two chapters on arylations, which involve arynes or radicals as key intermediates, and a summary of photochemically initiated transformations. I hope that this topical selection will be useful to the reader, and that it will serve as a stimulus for further exciting developments in this rapidly evolving research area.
Contents
Preface
List of Contributors
Arylation Reactions: A Historical Perspective
Lutz Ackermann
Structure and Bonding of Benzene
Syntheses of Substituted (Hetero)Arenes, and the Contents of this Book
Abbreviations
References
Metal-Catalyzed Coupling Reactions with Aryl Chlorides, Tosylates and Fluorides
Adam Littke
Introduction
Coupling Reactions of Aryl Chlorides
Nickel-Catalyzed Cross-Couplings of Aryl Chlorides
Palladium-Catalyzed Cross-Coupling Reactions
Suzuki Reaction
Stille Reaction
Hiyama Coupling
Negishi Coupling
Kumada Coupling
Coupling Reactions of Aryl Fluorides
Coupling Reactions of Aryl Tosylates
Conclusions
Abbreviations
References
Palladium-Catalyzed Arylations of Amines and ?-C–H Acidic Compounds
Bjц Schlummer and Ulrich Scholz
Introduction
Palladium-Catalyzed Arylations of Amines
Historical Development
Catalytic Systems
Palladium Sources
Ligands
Bases
Solvents
Aryl Halides
Arylsulfonic Acid Esters
Heteroaromatic Electrophiles
Amines as Nucleophiles
Amine Derivatives as Nucleophiles
Applications
Mechanistic Aspects
Chirality
Palladium-Catalyzed Arylations of ?-C–H Acidic Compounds
Historical Development
Catalytic Systems
?-Arylations of Esters
?-Arylations of Malonates and ?-Cyano Esters
?-Arylations of Ketones
?-Arylations of Amides
?-Arylations of Nitriles
Summary and Conclusions
Abbreviations
References
Copper-Catalyzed Arylations of Amines and Alcohols with Boron-Based Arylating Reagents
Andrew W. Thomas and Steven V. Ley
Introduction
Discovery and Development of a New O–H Bond Arylation Reaction: From Stoichiometric to Catalytic in Copper
Mechanistic Considerations
Miscellaneous Applications
Additional Applications with ArB(OH)2
Alteatives to ArB(OH)2
Alteatives to Phenols
Development of a New N–H Bond Arylation Reaction
Stoichiometric in Copper
Alteatives to Boronic Acids
Development of a New N–H Bond Arylation Reaction: Catalytic in Copper
Proposed Mechanism
Additional Important Non-N–H Arylation Examples
Summary and Conclusions
Abbreviations
References
Metal-Catalyzed Arylations of Nonactivated Alkyl (Pseudo)Halides via Cross-Coupling Reactions
Masaharu Nakamura and Shingo Ito
Introduction
Palladium-Catalyzed Arylations of Alkyl (Pseudo)Halides
Nickel-Catalyzed Arylations of Alkyl (Pseudo)Halides
Iron-Catalyzed Arylations of Alkyl (Pseudo)Halides
Copper- and Cobalt-Catalyzed Arylations of Alkyl (Pseudo)Halides
Abbreviations
References
Arylation Reactions of Alkynes: The Sonogashira Reaction
Mihai S. Viciu and Steven P. Nolan
Introduction
Palladium-Catalyzed Reactions: Ligands and Reaction Protocols
Phosphine-Based Ligands
Copper-Free Catalytic Systems
Hemilabile Ligands
Ionic Liquids as Reaction Media
Reactions in Aqueous Media
Recyclable Phosphine-Based Catalytic Systems
N-Heterocyclic Carbene Ligands for Sonogashira Coupling
Palladacycles as Catalysts in Sonogashira Reactions
Nitrogen-Coordinating Ligands
Alteative Metal Catalysts
Nickel-Catalyzed Sonogashira Reaction
Ruthenium-Based Catalytic Systems
Indium-Based Catalytic Systems
Copper-Based Catalytic Systems
Mechanism of the Sonogashira Reaction
Palladium- and Copper-Based Catalytic Systems
Copper-Free Catalytic Systems
Concluding Remarks
Abbreviations
References
Palladium-Catalyzed Arylation Reactions of Alkenes (Mizoroki–Heck Reaction and Related Processes)
Verena T. Trepohl and Martin Oestreich
Introduction
Mizoroki–Heck Arylations
Mechanistic Considerations
Intermolecular Mizoroki–Heck Arylations
Intermolecular Arylations
Asymmetric Intermolecular Arylations
Directed Intermolecular Arylations
Intramolecular Mizoroki–Heck Arylations
Intramolecular Arylations
Asymmetric Intramolecular Arylations
Desymmetrizing Intramolecular Arylations
Reductive Mizoroki–Heck-Type Arylations
Mechanistic Considerations
Intermolecular Arylations: The Bicyclo[2.2.1]heptane Case
Reductive Mizoroki–Heck-Type Arylation in Action
Oxidative Mizoroki–Heck-Type Arylations
Mechanistic Considerations
Intermolecular C–C Bond Formation
Arenes as Nucleophiles
Hetarenes as Nucleophiles
Intramolecular C–C Bond Formation
Arenes as Nucleophiles
Hetarenes as Nucleophiles
Abbreviations
References
Mode Arylations of Carbonyl Compounds
Christian Defi eber and Erick M. Carreira
Introduction
Enantioselective Arylation of Aldehydes
Zinc-Mediated Asymmetric Arylation of Aldehydes
Rhodium-Catalyzed Asymmetric Arylation of Aldehydes
Enantioselective Arylation of Ketones
Enantioselective Arylation of Aryl-Alkyl-Substituted Ketones
Enantioselective Arylation of Isatins
Enantioselective Arylation of Trifl uoromethyl-Substituted Ketones
Enantioselective Arylation of Imines
Zinc-Mediated Enantioselective Phenylation of Imines
Rhodium-Catalyzed Enantioselective Arylation of Imines
Rhodium-Catalyzed Diastereoselective Arylation of Imines
Conjugate Asymmetric Arylation
Aryl Sources for the Conjugate Asymmetric Arylation
Ligand Systems
Conjugate Arylation with Diphosphine–Palladium(II) Complexes
Enantioselective Conjugate Arylation of ?,?-Unsaturated Aldehydes
Enantioselective Conjugate Arylation of Maleimides
Additional Acceptors for Rhodium/Diene-Catalyzed Conjugate Arylation
Enantioselective Conjugate Arylation of 2,3-Dihydro-4-Pyridones
Enantioselective Conjugate Arylation of Coumarins
Conjugate Arylation of Chiral, Racemic ?,?-Unsaturated Carbonyl Compounds
Conjugate Asymmetric Arylation of 3-Substituted ?,?–unsaturated Carbonyl Compounds
1,6-Addition of Arylboronic Acids to ?,?,?,?-Unsaturated Carbonyl Compounds
Tandem Processes
Rhodium-Catalyzed Enantioselective Conjugate Arylation–Protonation
Rhodium-Catalyzed Conjugate Arylation–Aldol-Addition
Rhodium-Catalyzed Conjugate Arylation–Allylation
Rhodium-Catalyzed Sequential Carbometallation–Addition
Enantioselective Friedel–Crafts Arylation
Metal-Catalyzed Enantioselective Friedel–Crafts Arylations
Organocatalysis in Friedel–Crafts Arylation
Conclusions
Abbreviations
References
Metal-Catalyzed Direct Arylations (excluding Palladium)
Lutz Ackermann and Rubйn Vicente
Introduction
Rhodium-Catalyzed Direct Arylations
Rhodium-Catalyzed Direct Arylations of Arenes
Rhodium-Catalyzed Direct Arylations of Heteroarenes
Ruthenium-Catalyzed Direct Arylations
Ruthenium-Catalyzed Direct Arylations with Organometallic Reagents
Ruthenium-Catalyzed Direct Arylations with Aryl (Pseudo) Halides
Iridium-, Copper- and Iron-Catalyzed Direct Arylations
Conclusions
Abbreviations
References
Palladium-Catalyzed Direct Arylation Reactions
Masahiro Miura and Tetsuya Satoh
Introduction
Intermolecular Arylation of Functionalized Arenes
Reaction of Phenols and Benzyl Alcohols
Reaction of Aromatic Carbonyl and Pyridyl Compounds
Reaction of Miscellaneous Aromatic Substrates
Intramolecular Reaction of Haloaryl-Linked Arenes
Intermolecular Arylation Reactions of Heteroaromatic Compounds
Reaction of Pyrroles, Furans and Thiophenes
Reaction of Imidazoles, Oxazoles and Thiazoles
Reaction of Six-Membered Nitrogen Heterocycles
Concluding Remarks
Abbreviations
References
Mechanistic Aspects of Transition Metal-Catalyzed Direct Arylation Reactions
Paula de Mendoza and Antonio M. Echavarren
Introduction
Palladium-Catalyzed Intramolecular Direct Arylation
Intermolecular Metal-Catalyzed Direct Arylation of Arenes
Metal-Catalyzed Heteroaryl–Aryl and Heteroaryl–Heteroaryl Bond Formation
Direct Arylation via Metallacycles
Cross-Dehydrogenative Couplings
Summary
Abbreviations
References
Arylation Reactions Involving the Formation of Arynes
Yu Chen and Richard C. Larock
Introduction
Generation of Arynes
Electrophilic Coupling of Arynes
Formation of Monosubstituted Arenes by Proton Abstraction
Aryne Insertion into a Nucleophilic–Electrophilic ?-Bond
Three-Component Coupling Reactions via Aryl Carbanion Trapping by an Exteal Electrophile
Miscellaneous
Pericyclic Reactions of Arynes
Diels–Alder Reactions
[2+2] Cycloadditions
[3+2] Cycloadditions
Ene Reaction
Miscellaneous
Transition Metal-Catalyzed Reactions of Arynes
Transition Metal-Catalyzed Cyclizations
Palladium/Nickel-Catalyzed [2+2+2] Cycloadditions
Palladium-Catalyzed Cyclization Involving Carbopalladation of Arynes
Transition Metal-Catalyzed Carbonylations
Miscellaneous
Transition Metal-Catalyzed Coupling Reactions
Insertion of Arynes into ?-Bonds
Three-Component Coupling of Arynes Involving Carbopalladation
Summary
Abbreviations
References
Radical-Based Arylation Methods
Santiago E. Vaillard, Birte Schulte and Armido Studer
Introduction
SRN1-Type Radical Arylations
Intermolecular SRN1 Reactions
Intramolecular SRN1 Reactions
Homolytic Aromatic Substitutions
Intramolecular Homolytic Aromatic Substitutions
Arylations Using Nucleophilic C-Centered Radicals
Arylations Using Electrophilic C-Centered Radicals
Radical Aryl Migration Reactions
Intermolecular Homolytic Aromatic Substitutions
Arylation with Nucleophilic C-Centered Radicals
Arylation with Electrophilic C-Centered Radicals
Intermolecular ipso-Substitutions
Arylations Using Aryl Radicals
Additions onto Olefi ns: Meerwein Arylation
Cyclizations Using Aryl Radicals
Phosphonylation of Aryl Radicals
Conclusions
Abbreviations
References
Photochemical Arylation Reactions
Valentina Dichiarante, Maurizio Fagnoni and Angelo Albini
Introduction
Photochemical Formation of Aryl–C Bonds
Intermolecular Formation of Aryl–Alkyl Bonds
Cyanations
Intramolecular Formation of Aryl–Alkyl Bonds
Intermolecular Formation of Aryl–Aryl Bonds
Intramolecular Formation of Aryl–Aryl Bonds
Photochemical Formation of Aryl–N Bonds
Conclusions
Abbreviations
References
Index
Arenes and heteroarenes are essential substructures of numerous compounds with activities that are relevant to a variety of important areas of research, ranging inter alia from medicinal chemistry and biology to materials sciences. As a result, the selective preparation of these omnipresent moieties is of the utmost relevance to synthetic chemists, both in industry and academia.
Within the book, following a brief introduction, industrial practitioners review important transition metal - catalyzed cross - coupling reactions, as well as carbon – heteroatom bond - forming processes. The infl uence of catalytic strategies – and particularly of those that employ transition metal complexes – on arylation reactions with haloalkanes, alkenes, alkynes and carbonyl compounds as substrates is subsequently described. The next three chapters detail not only the experimental observations but also the mechanistic considerations of ecologically benign C – H bond functionalization reactions. Finally, the book concludes with two chapters on arylations, which involve arynes or radicals as key intermediates, and a summary of photochemically initiated transformations. I hope that this topical selection will be useful to the reader, and that it will serve as a stimulus for further exciting developments in this rapidly evolving research area.
Contents
Preface
List of Contributors
Arylation Reactions: A Historical Perspective
Lutz Ackermann
Structure and Bonding of Benzene
Syntheses of Substituted (Hetero)Arenes, and the Contents of this Book
Abbreviations
References
Metal-Catalyzed Coupling Reactions with Aryl Chlorides, Tosylates and Fluorides
Adam Littke
Introduction
Coupling Reactions of Aryl Chlorides
Nickel-Catalyzed Cross-Couplings of Aryl Chlorides
Palladium-Catalyzed Cross-Coupling Reactions
Suzuki Reaction
Stille Reaction
Hiyama Coupling
Negishi Coupling
Kumada Coupling
Coupling Reactions of Aryl Fluorides
Coupling Reactions of Aryl Tosylates
Conclusions
Abbreviations
References
Palladium-Catalyzed Arylations of Amines and ?-C–H Acidic Compounds
Bjц Schlummer and Ulrich Scholz
Introduction
Palladium-Catalyzed Arylations of Amines
Historical Development
Catalytic Systems
Palladium Sources
Ligands
Bases
Solvents
Aryl Halides
Arylsulfonic Acid Esters
Heteroaromatic Electrophiles
Amines as Nucleophiles
Amine Derivatives as Nucleophiles
Applications
Mechanistic Aspects
Chirality
Palladium-Catalyzed Arylations of ?-C–H Acidic Compounds
Historical Development
Catalytic Systems
?-Arylations of Esters
?-Arylations of Malonates and ?-Cyano Esters
?-Arylations of Ketones
?-Arylations of Amides
?-Arylations of Nitriles
Summary and Conclusions
Abbreviations
References
Copper-Catalyzed Arylations of Amines and Alcohols with Boron-Based Arylating Reagents
Andrew W. Thomas and Steven V. Ley
Introduction
Discovery and Development of a New O–H Bond Arylation Reaction: From Stoichiometric to Catalytic in Copper
Mechanistic Considerations
Miscellaneous Applications
Additional Applications with ArB(OH)2
Alteatives to ArB(OH)2
Alteatives to Phenols
Development of a New N–H Bond Arylation Reaction
Stoichiometric in Copper
Alteatives to Boronic Acids
Development of a New N–H Bond Arylation Reaction: Catalytic in Copper
Proposed Mechanism
Additional Important Non-N–H Arylation Examples
Summary and Conclusions
Abbreviations
References
Metal-Catalyzed Arylations of Nonactivated Alkyl (Pseudo)Halides via Cross-Coupling Reactions
Masaharu Nakamura and Shingo Ito
Introduction
Palladium-Catalyzed Arylations of Alkyl (Pseudo)Halides
Nickel-Catalyzed Arylations of Alkyl (Pseudo)Halides
Iron-Catalyzed Arylations of Alkyl (Pseudo)Halides
Copper- and Cobalt-Catalyzed Arylations of Alkyl (Pseudo)Halides
Abbreviations
References
Arylation Reactions of Alkynes: The Sonogashira Reaction
Mihai S. Viciu and Steven P. Nolan
Introduction
Palladium-Catalyzed Reactions: Ligands and Reaction Protocols
Phosphine-Based Ligands
Copper-Free Catalytic Systems
Hemilabile Ligands
Ionic Liquids as Reaction Media
Reactions in Aqueous Media
Recyclable Phosphine-Based Catalytic Systems
N-Heterocyclic Carbene Ligands for Sonogashira Coupling
Palladacycles as Catalysts in Sonogashira Reactions
Nitrogen-Coordinating Ligands
Alteative Metal Catalysts
Nickel-Catalyzed Sonogashira Reaction
Ruthenium-Based Catalytic Systems
Indium-Based Catalytic Systems
Copper-Based Catalytic Systems
Mechanism of the Sonogashira Reaction
Palladium- and Copper-Based Catalytic Systems
Copper-Free Catalytic Systems
Concluding Remarks
Abbreviations
References
Palladium-Catalyzed Arylation Reactions of Alkenes (Mizoroki–Heck Reaction and Related Processes)
Verena T. Trepohl and Martin Oestreich
Introduction
Mizoroki–Heck Arylations
Mechanistic Considerations
Intermolecular Mizoroki–Heck Arylations
Intermolecular Arylations
Asymmetric Intermolecular Arylations
Directed Intermolecular Arylations
Intramolecular Mizoroki–Heck Arylations
Intramolecular Arylations
Asymmetric Intramolecular Arylations
Desymmetrizing Intramolecular Arylations
Reductive Mizoroki–Heck-Type Arylations
Mechanistic Considerations
Intermolecular Arylations: The Bicyclo[2.2.1]heptane Case
Reductive Mizoroki–Heck-Type Arylation in Action
Oxidative Mizoroki–Heck-Type Arylations
Mechanistic Considerations
Intermolecular C–C Bond Formation
Arenes as Nucleophiles
Hetarenes as Nucleophiles
Intramolecular C–C Bond Formation
Arenes as Nucleophiles
Hetarenes as Nucleophiles
Abbreviations
References
Mode Arylations of Carbonyl Compounds
Christian Defi eber and Erick M. Carreira
Introduction
Enantioselective Arylation of Aldehydes
Zinc-Mediated Asymmetric Arylation of Aldehydes
Rhodium-Catalyzed Asymmetric Arylation of Aldehydes
Enantioselective Arylation of Ketones
Enantioselective Arylation of Aryl-Alkyl-Substituted Ketones
Enantioselective Arylation of Isatins
Enantioselective Arylation of Trifl uoromethyl-Substituted Ketones
Enantioselective Arylation of Imines
Zinc-Mediated Enantioselective Phenylation of Imines
Rhodium-Catalyzed Enantioselective Arylation of Imines
Rhodium-Catalyzed Diastereoselective Arylation of Imines
Conjugate Asymmetric Arylation
Aryl Sources for the Conjugate Asymmetric Arylation
Ligand Systems
Conjugate Arylation with Diphosphine–Palladium(II) Complexes
Enantioselective Conjugate Arylation of ?,?-Unsaturated Aldehydes
Enantioselective Conjugate Arylation of Maleimides
Additional Acceptors for Rhodium/Diene-Catalyzed Conjugate Arylation
Enantioselective Conjugate Arylation of 2,3-Dihydro-4-Pyridones
Enantioselective Conjugate Arylation of Coumarins
Conjugate Arylation of Chiral, Racemic ?,?-Unsaturated Carbonyl Compounds
Conjugate Asymmetric Arylation of 3-Substituted ?,?–unsaturated Carbonyl Compounds
1,6-Addition of Arylboronic Acids to ?,?,?,?-Unsaturated Carbonyl Compounds
Tandem Processes
Rhodium-Catalyzed Enantioselective Conjugate Arylation–Protonation
Rhodium-Catalyzed Conjugate Arylation–Aldol-Addition
Rhodium-Catalyzed Conjugate Arylation–Allylation
Rhodium-Catalyzed Sequential Carbometallation–Addition
Enantioselective Friedel–Crafts Arylation
Metal-Catalyzed Enantioselective Friedel–Crafts Arylations
Organocatalysis in Friedel–Crafts Arylation
Conclusions
Abbreviations
References
Metal-Catalyzed Direct Arylations (excluding Palladium)
Lutz Ackermann and Rubйn Vicente
Introduction
Rhodium-Catalyzed Direct Arylations
Rhodium-Catalyzed Direct Arylations of Arenes
Rhodium-Catalyzed Direct Arylations of Heteroarenes
Ruthenium-Catalyzed Direct Arylations
Ruthenium-Catalyzed Direct Arylations with Organometallic Reagents
Ruthenium-Catalyzed Direct Arylations with Aryl (Pseudo) Halides
Iridium-, Copper- and Iron-Catalyzed Direct Arylations
Conclusions
Abbreviations
References
Palladium-Catalyzed Direct Arylation Reactions
Masahiro Miura and Tetsuya Satoh
Introduction
Intermolecular Arylation of Functionalized Arenes
Reaction of Phenols and Benzyl Alcohols
Reaction of Aromatic Carbonyl and Pyridyl Compounds
Reaction of Miscellaneous Aromatic Substrates
Intramolecular Reaction of Haloaryl-Linked Arenes
Intermolecular Arylation Reactions of Heteroaromatic Compounds
Reaction of Pyrroles, Furans and Thiophenes
Reaction of Imidazoles, Oxazoles and Thiazoles
Reaction of Six-Membered Nitrogen Heterocycles
Concluding Remarks
Abbreviations
References
Mechanistic Aspects of Transition Metal-Catalyzed Direct Arylation Reactions
Paula de Mendoza and Antonio M. Echavarren
Introduction
Palladium-Catalyzed Intramolecular Direct Arylation
Intermolecular Metal-Catalyzed Direct Arylation of Arenes
Metal-Catalyzed Heteroaryl–Aryl and Heteroaryl–Heteroaryl Bond Formation
Direct Arylation via Metallacycles
Cross-Dehydrogenative Couplings
Summary
Abbreviations
References
Arylation Reactions Involving the Formation of Arynes
Yu Chen and Richard C. Larock
Introduction
Generation of Arynes
Electrophilic Coupling of Arynes
Formation of Monosubstituted Arenes by Proton Abstraction
Aryne Insertion into a Nucleophilic–Electrophilic ?-Bond
Three-Component Coupling Reactions via Aryl Carbanion Trapping by an Exteal Electrophile
Miscellaneous
Pericyclic Reactions of Arynes
Diels–Alder Reactions
[2+2] Cycloadditions
[3+2] Cycloadditions
Ene Reaction
Miscellaneous
Transition Metal-Catalyzed Reactions of Arynes
Transition Metal-Catalyzed Cyclizations
Palladium/Nickel-Catalyzed [2+2+2] Cycloadditions
Palladium-Catalyzed Cyclization Involving Carbopalladation of Arynes
Transition Metal-Catalyzed Carbonylations
Miscellaneous
Transition Metal-Catalyzed Coupling Reactions
Insertion of Arynes into ?-Bonds
Three-Component Coupling of Arynes Involving Carbopalladation
Summary
Abbreviations
References
Radical-Based Arylation Methods
Santiago E. Vaillard, Birte Schulte and Armido Studer
Introduction
SRN1-Type Radical Arylations
Intermolecular SRN1 Reactions
Intramolecular SRN1 Reactions
Homolytic Aromatic Substitutions
Intramolecular Homolytic Aromatic Substitutions
Arylations Using Nucleophilic C-Centered Radicals
Arylations Using Electrophilic C-Centered Radicals
Radical Aryl Migration Reactions
Intermolecular Homolytic Aromatic Substitutions
Arylation with Nucleophilic C-Centered Radicals
Arylation with Electrophilic C-Centered Radicals
Intermolecular ipso-Substitutions
Arylations Using Aryl Radicals
Additions onto Olefi ns: Meerwein Arylation
Cyclizations Using Aryl Radicals
Phosphonylation of Aryl Radicals
Conclusions
Abbreviations
References
Photochemical Arylation Reactions
Valentina Dichiarante, Maurizio Fagnoni and Angelo Albini
Introduction
Photochemical Formation of Aryl–C Bonds
Intermolecular Formation of Aryl–Alkyl Bonds
Cyanations
Intramolecular Formation of Aryl–Alkyl Bonds
Intermolecular Formation of Aryl–Aryl Bonds
Intramolecular Formation of Aryl–Aryl Bonds
Photochemical Formation of Aryl–N Bonds
Conclusions
Abbreviations
References
Index