WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007. - 573 p.
Although nowadays almost anybody seems to know something about the Claisen rearrangement, the exact nature of the transition state and the way substituents and solvents influence the rate and the selectivity of the reaction can be very difficult to elucidate. However, for the vast majority of applications, qualitative guidelines are sufficient to predict and/or explain the course of a Claisen rearrangement. One of the main conclusions from this book is that there isn’t the Claisen rearrangement but a truly amazing number of mechanistically related variations of it that have been and are being developed. In this context, the first Claisen book presents a platform conceing basics and the state of the art.
Contents
Preface
List of Contributors
Chorismate-Mutase-Catalyzed Claisen Rearrangement
Hong Guo and Niny Rao
Introduction
Experimental Studies
Substrate Binding
Substrate Structural Requirements for Catalysis
X-ray Structures of Chorismate Mutase
Effects of Mutations
Activation Parameters
Catalytic Mechanism of Chorismate Mutase
Stabilization of Transition State by Active Site Residues
Substrate Conformational Transition and the Role of Active Site Residues
Contribution of the Near Attack Conformers (NACs)
Strain Effects and Conformational Compression
Conclusion
References
Chiral-Metal-Complex-Catalyzed Aliphatic Claisen Rearrangement 25
Koichi Mikami and Katsuhiro Akiyama
Introduction
Binding Modes of Main-group and Late Transition Metals
Aluminum(III)-promoted Claisen Rearrangement
Copper(II)-catalyzed Claisen Rearrangement
Palladium(II)-catalyzed Claisen Rearrangement
References
Aliphatic and Aromatic Claisen Rearrangement
Hayato Ichikawa and Keiji Maruoka
Aliphatic Claisen Rearrangement
Introduction
Synthesis of Allyl Vinyl Ethers
Hg-Catalyzed Synthesis
From Ammonium Betaine
Acid-Catalyzed Synthesis
Wittig Olefination
Sulfoxide Elimination
Selenoxide Elimination
From Ketal
From Allene
Ir-Catalyzed Synthesis
Cu-Catalyzed Synthesis
Tebbe Reagent
Acyclic Aliphatic Claisen Rearrangement
Transition State of Aliphatic Claisen Rearrangement
Secondary Allylic Ethers
Substituted Vinyl Ethers
Allyl Allenyl Ethers
Disubstituted Vinyl Ether
Water-Promoted Claisen Rearrangement
Diastereoselective Rearrangement Using Chiral Sulfoxide Groups
Claisen Rearrangement of Cyclic Allyl Vinyl Ethers
Ring Expansion Claisen Rearrangement
Cyclohexene Synthesis
Cyclic Vinyl Ethers
Cyclic Allyl Ethers
Tandem Reactions Including Aliphatic Claisen Rearrangement
Vinylation/Claisen Rearrangement
Allylation/Claisen Rearrangement
Anionic Cyclization/Claisen Rearrangement
Claisen Rearrangement/Ene Reaction
Claisen Rearrangement/Conia-Type Oxa-Ene Reaction
Oxy-Cope/Ene/Claisen Rearrangement
The Carbanion-Accelerated Claisen Rearrangement
Sulfonyl-Stabilized Anions
Phosphine Oxide and Phosphonate-Stabilized Anions
Phosphonamide-Stabilized Anions
Conclusion
References
Aromatic Claisen Rearrangement
Hisanaka Ito and Takeo Taguchi
Introduction
Mechanism
Ortho and Para Rearrangement
Transition State
Abnormal Claisen Rearrangement
Substrate and Substituent Effect
Preparation of Substrate
Aryl Unit
Allyl and Propargyl Unit
Reaction Conditions
Thermal Conditions
Solvent Effect
Brшnsted Acid Catalyst
Lewis Acid Catalyst
Base Catalyst
Transition Metal Catalyst
Other Conditions
Thio-, Amino-, and Related Claisen Rearrangement
Asymmetric Synthesis
Intramolecular Chirality Transfer
Enantioselective Rearrangement
Synthetic Applications
Consecutive Cyclization
Tandem Reaction
Functional Molecule
Natural Products and Biologically Active Compounds
Reference
The Ireland–Claisen Rearrangement (1972–2004)
Christopher M. McFarland and Matthias C. McIntosh
Introduction
History
Numbering and Nomenclature
Rearrangement Temperature, Substituent Effects and Catalysis
Rearrangement Temperature
Substituent Effects
Catalysis
Pd(II) Catalysis
Lewis Acid Catalysis
Phosphine Catalysis
Transition State Structure
Isotope Effect Studies
Deuterium Isotope Effects
14C Isotope Effects
Theoretical Studies
Calculated vs. Experimental Isotope Effects and Transition State Structure
Cyclohexenyl Allyl Methyl Ketene Acetals
Stereochemical Aspects
Simple Diastereoselection: Chair vs. Boat Transition States
Enolate and Silyl Ketene Acetal Geometry
Acyclic Allyl Silyl Ketene Acetals
Diastereoface Differentiation: Cyclic Allyl Silyl Ketene Acetals
Alkene Stereochemistry
Chirality Transfer
Allylic Esters Possessing One Stereocenter: Absolute Stereocontrol
Allylic Esters Possessing Multiple Stereocenters: Relative Stereocontrol
Influence of Remote Stereocenters
C1? Stereocenters
C5? Stereocenters
C6? Stereocenters
Other Remote Stereocenters
Chiral Auxiliary Mediated Asymmetric Ireland – Claisen Rearrangements
Chiral Glycolates
Chiral Glycinates
Chiral Boron Ketene Acetals
Methods of Ketene Acetal Formation
Chemoselective Deprotonations
Ester vs. Ketone
Ester vs. Butenolide
Ester vs. Branched Ester
c-Deprotonations of Allyl Acrylates
Silyl Triflates and Tertiary Amine Bases
N,O-Bis(trimethylsilyl)acetamide and CuOTf
1,4-Additions
By Alkyl Cu Reagents
By Alkyl Radicals
By Enolates
By Silanes
Electrochemical Reduction
Diels – Alder Cycloaddition
Brook Rearrangement
Boron Ketene Acetals
Post-Rearrangement Enolization
Structural Variations in Allylic Esters
Allylic Esters with ?-Heteroatoms
Glycolates
Lactates
Mandelates
Other Higher Esters
Glycinates and Other Higher Esters
Allyl Silanes and Stannanes
Glycals
Allyl Lactones
Lactones with Exocyclic Allylic Alkenes
Lactones with Endocyclic Allylic Alkenes
Tertiary Alcohol-Derived Allylic Esters
bis-Allylic Esters
Fe-Diene Complexes
Hindered Esters
Applications to Natural Product Synthesis
Prostanoids
Nonactic Acid
Lasalocid A
Tirandamycic Acid
Monensin A
Sphydofuran
Calcimycin
Ceroplasteric Acid
Erythronolide A
Ebelactone A and B
25-OH Vitamin D2 Grundmann Ketone
Zincophorin
Steroid Side Chain Homologation
Pseudomonic Acid C
Pine Sawfly Pheromone
Asteltoxin
Breynolide
Methyl Ydiginate
(–)-Petasinecine
b-Elemene
(+)-Dolabellatrienone
2-Keto-3-Deoxy-Octonic Acid (KDO)
Methylenolactocin
Eupomatilones
Trichothecenes
(±)-Widdrol
Equisetin
Muscone
Quadrone
Ingenanes
(±)-Samin
(+)-Monomorine
Dictyols
Propargyl Esters
Conclusion
References
Simple and Chelate Enolate Claisen Rearrangement
Simple Enolate Claisen Rearrangement
Mukund G. Kulkai
Introduction
History
Simple Enolates of Allylic Esters
Stereoselectivity in Enolate Formation
Simple Enolates of Allylic Esters of ?-Hetero Acids
Simple Enolates of N-Allyl Amides
Miscellaneous Enolates
Conclusion
References
Chelate Enolate Claisen Rearrangement
Uli Kazmaier
Introduction
Claisen Rearrangements of Substrates with Chelating Substituents in the ?-Position
Rearrangement of ?-Hydroxy Substituted Allylic Esters
Rearrangement of ?-Alkoxy-Substituted Allylic Esters
?-Amido Substituents
Rearrangement of ?-Thio Substituted Allylic Esters
Claisen Rearrangements of Substrates Bearing Chelating Substituents in the b-Position
b-Hydroxy Substituents
b-Alkoxy Substitutents
b-Amino Substituted Substrates
Chelation Controlled Aza-Claisen Rearrangements
References
Claisen–Johnson Orthoester Rearrangement
Yves Langlois
Introduction
Historical Overview
Mechanistic Aspects
Reactivity
Stereoselectivity
Alteatives to the Orthoester Rearrangement
Synthetic Applications
Terpenes, Fatty Acids, and Polyketide Derivatives Steroids
Syntheses of the Tetracyclic Core of Steroids
Syntheses of Steroid Side Chains
Alkaloids
Indole Alkaloids
Other Alkaloids
Carbohydrates
Miscellaneous Compounds
Conclusion
References
The Meerwein–Eschenmoser–Claisen Rearrangement
Stefan N. Gradl and Dirk Trauner
Definition, Discovery and Scope
Formation of Ketene N,O-Acetals
Condensation with Amide Acetals or Ketene Acetals (Eschenmoser – Claisen Rearrangement)
Addition of Alkoxides to Amidinium Ions (Meerwein – Claisen Rearrangement)
Addition of Alcohols to Ynamines and Ynamides (Ficini – Claisen Rearrangement)
Miscellaneous Methods
Selectivity
Regioselectivity
Stereoselectivity
Cyclic Allylic Alcohols
Acyclic Allylic Alcohols
Applications in Synthesis
References
The Carroll Rearrangement
Mark A. Hatcher and Gary H. Posner
Introduction
Mechanism
Synthetic Applications
Tertiary and Quateary Carbon Bond Formation
Natural Products
Steroidal Side-Chain Formation
Aromatic Carroll Rearrangements
Carroll Variants
?-Sulfonyl Carroll Rearrangement
Asymmetric Carroll Rearrangement
Metal-Catalyzed Carroll Rearrangement
Conclusion
References
Thio-Claisen Rearrangement
Stйphane Perrio, Vincent Reboul, Carole Alayrac, and Patrick Metzner
Introduction
Early Developments
Aromatic and Heteroaromatic Series
Aliphatic Series
Specificities of the Sulfur Version – Kinetics Versus Thermodynamics
Reviews
Basic Versions
Flexible Synthesis of the Substrates
Scope and Limitations, Reaction Conditions
Synthesis of Unsaturated Aldehydes (via Transient Thioaldehydes)
Thioketones
Dithioesters
Thionesters
Thioamides
Thioketenes
Rearrangement of Tricoordinated Sulfur Derivatives: Sulfonium Salts or Sulfoxides
Catalysis
Rearrangement with Stereochemical Control
Relative Control Exclusively Through Double-Bond Configurations
Control Through an Asymmetric Carbon Center
Stereogenic Sulfur Center
Cyclic Chiral Auxiliary
Axial Chirality
Applications in Organic Synthesis
Synthesis of Heterocycles
Synthesis of Natural Products and Construction of Building Blocks
Conclusion
References
Aza-Claisen Rearrangement
Udo Nubbemeyer
Introduction 461
Aromatic Simple Aza-Claisen Rearrangements
Aliphatic Simple Aza-Claisen Rearrangements
Amide Acetal and Amide Enolate Claisen Rearrangements
Zwitterionic Aza-Claisen Rearrangements
Alkyne Carbonester Aza-Claisen Rearrangements
Ketene Aza-Claisen Rearrangements
Allene Carbonester Aza-Claisen Rearrangements
Alkyne Aza-Claisen Rearrangements
Iminoketene Claisen Rearrangements
References
Mechanistic Aspects of the Aliphatic Claisen Rearrangement
Julia Rehbein and Martin Hiersemann
References
Subject Index
Although nowadays almost anybody seems to know something about the Claisen rearrangement, the exact nature of the transition state and the way substituents and solvents influence the rate and the selectivity of the reaction can be very difficult to elucidate. However, for the vast majority of applications, qualitative guidelines are sufficient to predict and/or explain the course of a Claisen rearrangement. One of the main conclusions from this book is that there isn’t the Claisen rearrangement but a truly amazing number of mechanistically related variations of it that have been and are being developed. In this context, the first Claisen book presents a platform conceing basics and the state of the art.
Contents
Preface
List of Contributors
Chorismate-Mutase-Catalyzed Claisen Rearrangement
Hong Guo and Niny Rao
Introduction
Experimental Studies
Substrate Binding
Substrate Structural Requirements for Catalysis
X-ray Structures of Chorismate Mutase
Effects of Mutations
Activation Parameters
Catalytic Mechanism of Chorismate Mutase
Stabilization of Transition State by Active Site Residues
Substrate Conformational Transition and the Role of Active Site Residues
Contribution of the Near Attack Conformers (NACs)
Strain Effects and Conformational Compression
Conclusion
References
Chiral-Metal-Complex-Catalyzed Aliphatic Claisen Rearrangement 25
Koichi Mikami and Katsuhiro Akiyama
Introduction
Binding Modes of Main-group and Late Transition Metals
Aluminum(III)-promoted Claisen Rearrangement
Copper(II)-catalyzed Claisen Rearrangement
Palladium(II)-catalyzed Claisen Rearrangement
References
Aliphatic and Aromatic Claisen Rearrangement
Hayato Ichikawa and Keiji Maruoka
Aliphatic Claisen Rearrangement
Introduction
Synthesis of Allyl Vinyl Ethers
Hg-Catalyzed Synthesis
From Ammonium Betaine
Acid-Catalyzed Synthesis
Wittig Olefination
Sulfoxide Elimination
Selenoxide Elimination
From Ketal
From Allene
Ir-Catalyzed Synthesis
Cu-Catalyzed Synthesis
Tebbe Reagent
Acyclic Aliphatic Claisen Rearrangement
Transition State of Aliphatic Claisen Rearrangement
Secondary Allylic Ethers
Substituted Vinyl Ethers
Allyl Allenyl Ethers
Disubstituted Vinyl Ether
Water-Promoted Claisen Rearrangement
Diastereoselective Rearrangement Using Chiral Sulfoxide Groups
Claisen Rearrangement of Cyclic Allyl Vinyl Ethers
Ring Expansion Claisen Rearrangement
Cyclohexene Synthesis
Cyclic Vinyl Ethers
Cyclic Allyl Ethers
Tandem Reactions Including Aliphatic Claisen Rearrangement
Vinylation/Claisen Rearrangement
Allylation/Claisen Rearrangement
Anionic Cyclization/Claisen Rearrangement
Claisen Rearrangement/Ene Reaction
Claisen Rearrangement/Conia-Type Oxa-Ene Reaction
Oxy-Cope/Ene/Claisen Rearrangement
The Carbanion-Accelerated Claisen Rearrangement
Sulfonyl-Stabilized Anions
Phosphine Oxide and Phosphonate-Stabilized Anions
Phosphonamide-Stabilized Anions
Conclusion
References
Aromatic Claisen Rearrangement
Hisanaka Ito and Takeo Taguchi
Introduction
Mechanism
Ortho and Para Rearrangement
Transition State
Abnormal Claisen Rearrangement
Substrate and Substituent Effect
Preparation of Substrate
Aryl Unit
Allyl and Propargyl Unit
Reaction Conditions
Thermal Conditions
Solvent Effect
Brшnsted Acid Catalyst
Lewis Acid Catalyst
Base Catalyst
Transition Metal Catalyst
Other Conditions
Thio-, Amino-, and Related Claisen Rearrangement
Asymmetric Synthesis
Intramolecular Chirality Transfer
Enantioselective Rearrangement
Synthetic Applications
Consecutive Cyclization
Tandem Reaction
Functional Molecule
Natural Products and Biologically Active Compounds
Reference
The Ireland–Claisen Rearrangement (1972–2004)
Christopher M. McFarland and Matthias C. McIntosh
Introduction
History
Numbering and Nomenclature
Rearrangement Temperature, Substituent Effects and Catalysis
Rearrangement Temperature
Substituent Effects
Catalysis
Pd(II) Catalysis
Lewis Acid Catalysis
Phosphine Catalysis
Transition State Structure
Isotope Effect Studies
Deuterium Isotope Effects
14C Isotope Effects
Theoretical Studies
Calculated vs. Experimental Isotope Effects and Transition State Structure
Cyclohexenyl Allyl Methyl Ketene Acetals
Stereochemical Aspects
Simple Diastereoselection: Chair vs. Boat Transition States
Enolate and Silyl Ketene Acetal Geometry
Acyclic Allyl Silyl Ketene Acetals
Diastereoface Differentiation: Cyclic Allyl Silyl Ketene Acetals
Alkene Stereochemistry
Chirality Transfer
Allylic Esters Possessing One Stereocenter: Absolute Stereocontrol
Allylic Esters Possessing Multiple Stereocenters: Relative Stereocontrol
Influence of Remote Stereocenters
C1? Stereocenters
C5? Stereocenters
C6? Stereocenters
Other Remote Stereocenters
Chiral Auxiliary Mediated Asymmetric Ireland – Claisen Rearrangements
Chiral Glycolates
Chiral Glycinates
Chiral Boron Ketene Acetals
Methods of Ketene Acetal Formation
Chemoselective Deprotonations
Ester vs. Ketone
Ester vs. Butenolide
Ester vs. Branched Ester
c-Deprotonations of Allyl Acrylates
Silyl Triflates and Tertiary Amine Bases
N,O-Bis(trimethylsilyl)acetamide and CuOTf
1,4-Additions
By Alkyl Cu Reagents
By Alkyl Radicals
By Enolates
By Silanes
Electrochemical Reduction
Diels – Alder Cycloaddition
Brook Rearrangement
Boron Ketene Acetals
Post-Rearrangement Enolization
Structural Variations in Allylic Esters
Allylic Esters with ?-Heteroatoms
Glycolates
Lactates
Mandelates
Other Higher Esters
Glycinates and Other Higher Esters
Allyl Silanes and Stannanes
Glycals
Allyl Lactones
Lactones with Exocyclic Allylic Alkenes
Lactones with Endocyclic Allylic Alkenes
Tertiary Alcohol-Derived Allylic Esters
bis-Allylic Esters
Fe-Diene Complexes
Hindered Esters
Applications to Natural Product Synthesis
Prostanoids
Nonactic Acid
Lasalocid A
Tirandamycic Acid
Monensin A
Sphydofuran
Calcimycin
Ceroplasteric Acid
Erythronolide A
Ebelactone A and B
25-OH Vitamin D2 Grundmann Ketone
Zincophorin
Steroid Side Chain Homologation
Pseudomonic Acid C
Pine Sawfly Pheromone
Asteltoxin
Breynolide
Methyl Ydiginate
(–)-Petasinecine
b-Elemene
(+)-Dolabellatrienone
2-Keto-3-Deoxy-Octonic Acid (KDO)
Methylenolactocin
Eupomatilones
Trichothecenes
(±)-Widdrol
Equisetin
Muscone
Quadrone
Ingenanes
(±)-Samin
(+)-Monomorine
Dictyols
Propargyl Esters
Conclusion
References
Simple and Chelate Enolate Claisen Rearrangement
Simple Enolate Claisen Rearrangement
Mukund G. Kulkai
Introduction
History
Simple Enolates of Allylic Esters
Stereoselectivity in Enolate Formation
Simple Enolates of Allylic Esters of ?-Hetero Acids
Simple Enolates of N-Allyl Amides
Miscellaneous Enolates
Conclusion
References
Chelate Enolate Claisen Rearrangement
Uli Kazmaier
Introduction
Claisen Rearrangements of Substrates with Chelating Substituents in the ?-Position
Rearrangement of ?-Hydroxy Substituted Allylic Esters
Rearrangement of ?-Alkoxy-Substituted Allylic Esters
?-Amido Substituents
Rearrangement of ?-Thio Substituted Allylic Esters
Claisen Rearrangements of Substrates Bearing Chelating Substituents in the b-Position
b-Hydroxy Substituents
b-Alkoxy Substitutents
b-Amino Substituted Substrates
Chelation Controlled Aza-Claisen Rearrangements
References
Claisen–Johnson Orthoester Rearrangement
Yves Langlois
Introduction
Historical Overview
Mechanistic Aspects
Reactivity
Stereoselectivity
Alteatives to the Orthoester Rearrangement
Synthetic Applications
Terpenes, Fatty Acids, and Polyketide Derivatives Steroids
Syntheses of the Tetracyclic Core of Steroids
Syntheses of Steroid Side Chains
Alkaloids
Indole Alkaloids
Other Alkaloids
Carbohydrates
Miscellaneous Compounds
Conclusion
References
The Meerwein–Eschenmoser–Claisen Rearrangement
Stefan N. Gradl and Dirk Trauner
Definition, Discovery and Scope
Formation of Ketene N,O-Acetals
Condensation with Amide Acetals or Ketene Acetals (Eschenmoser – Claisen Rearrangement)
Addition of Alkoxides to Amidinium Ions (Meerwein – Claisen Rearrangement)
Addition of Alcohols to Ynamines and Ynamides (Ficini – Claisen Rearrangement)
Miscellaneous Methods
Selectivity
Regioselectivity
Stereoselectivity
Cyclic Allylic Alcohols
Acyclic Allylic Alcohols
Applications in Synthesis
References
The Carroll Rearrangement
Mark A. Hatcher and Gary H. Posner
Introduction
Mechanism
Synthetic Applications
Tertiary and Quateary Carbon Bond Formation
Natural Products
Steroidal Side-Chain Formation
Aromatic Carroll Rearrangements
Carroll Variants
?-Sulfonyl Carroll Rearrangement
Asymmetric Carroll Rearrangement
Metal-Catalyzed Carroll Rearrangement
Conclusion
References
Thio-Claisen Rearrangement
Stйphane Perrio, Vincent Reboul, Carole Alayrac, and Patrick Metzner
Introduction
Early Developments
Aromatic and Heteroaromatic Series
Aliphatic Series
Specificities of the Sulfur Version – Kinetics Versus Thermodynamics
Reviews
Basic Versions
Flexible Synthesis of the Substrates
Scope and Limitations, Reaction Conditions
Synthesis of Unsaturated Aldehydes (via Transient Thioaldehydes)
Thioketones
Dithioesters
Thionesters
Thioamides
Thioketenes
Rearrangement of Tricoordinated Sulfur Derivatives: Sulfonium Salts or Sulfoxides
Catalysis
Rearrangement with Stereochemical Control
Relative Control Exclusively Through Double-Bond Configurations
Control Through an Asymmetric Carbon Center
Stereogenic Sulfur Center
Cyclic Chiral Auxiliary
Axial Chirality
Applications in Organic Synthesis
Synthesis of Heterocycles
Synthesis of Natural Products and Construction of Building Blocks
Conclusion
References
Aza-Claisen Rearrangement
Udo Nubbemeyer
Introduction 461
Aromatic Simple Aza-Claisen Rearrangements
Aliphatic Simple Aza-Claisen Rearrangements
Amide Acetal and Amide Enolate Claisen Rearrangements
Zwitterionic Aza-Claisen Rearrangements
Alkyne Carbonester Aza-Claisen Rearrangements
Ketene Aza-Claisen Rearrangements
Allene Carbonester Aza-Claisen Rearrangements
Alkyne Aza-Claisen Rearrangements
Iminoketene Claisen Rearrangements
References
Mechanistic Aspects of the Aliphatic Claisen Rearrangement
Julia Rehbein and Martin Hiersemann
References
Subject Index