Органическая химия
Химия и химическая промышленность
  • формат pdf
  • размер 9.9 МБ
  • добавлен 10 июня 2011 г.
Hiersemann M., Nubbemeyer U. (ed.) The Claisen Rearrangement. Methods and Applications
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
Смотрите также

Berthod A. (ed.) Chiral Recognition in Separation Methods. Mechanisms and Applications

  • формат pdf
  • размер 16.44 МБ
  • добавлен 18 июля 2011 г.
Springer. 2010. 352 p. The importance of chiral interactions for both preparative and analytical separations, particularly for pharmaceutical applications, is underlined by numerous publications in this field. Here, for the first time, a team of experienced analysts from industry and academe presents a comprehensive review of the various mechanisms that result in enantiomer separations. A better understanding of these processes is crucial for se...

Boger D.L. Modern Organic Synthesis

  • формат pdf
  • размер 9.44 МБ
  • добавлен 26 июня 2011 г.
TSRI Press. 1999. - 486 p. The notes have been used as the introductory section of a course on Modern Organic Synthesis that composes 6 weeks or a little more than one-half of a quarter course at The Scripps Research Institute, Department of Chemistry. Consequently, an exhaustive treatment of the individual topics is beyond the scope of this portion of the course. The remaining 4 weeks of the quarter delve into more detail on various topics and i...

Engel R., Cohen J.I. Synthesis of Carbon-Phosphorus Bonds

  • формат pdf
  • размер 5.17 МБ
  • добавлен 11 марта 2011 г.
CRC Press. 2004. 187 p. Introduction Synthesis of organophosphorus compounds from elemental phosphorus C-P bond formation using nucleophilic trivalent phosphorus reagents C-P bond formation bia displacement, addition, or rearrangement Pentacoordinate phosphorus Aromatic and vinylic C-P bonds

Grimmett M.R. Imidazole and Benzimidazole Synthesis

  • формат pdf
  • размер 9.15 МБ
  • добавлен 07 июня 2011 г.
Best synthetic methods. Sub-series: Key systems and functional groups.Academic Press. 1997. 265 p. Imidazoles and benzimidazoles are molecules of wide interest and importance, especially with regard to their pharmaceutical applications. This book surveys the known methods of synthesis and ring modification and presents recommendations for the most attractive synthetic approaches. It brings together the multitude of syntheses of the imidazole rin...

Gronowitz S., Hoernberg A.-B. Thiophenes

  • формат pdf
  • размер 13 МБ
  • добавлен 07 июня 2011 г.
Best synthetic methods. Elsevier. 2004. 964 p. This book is the product of the authors many years practical experience and reading of the original literature. It contains a valuable distillation and critical evaluation of the Best Synthetic Methods for the formation and reaction of thiophenes (five membered heterocycles containing a ring sulfur) or polymers containing a thiophene functionality (thienyls). A brief review of each area is provided,...

Harmata M. (ed.). Silver in Organic Chemistry

  • формат pdf
  • размер 8.98 МБ
  • добавлен 02 июня 2011 г.
John Wiley & Sons Inc. 2010. - 402 p. This book explores the use of silver in organic synthesis. Silver and its salts and complexes have figured significantly in the history of chemistry, recognized for their special conductive properties, use in photography, and even biological activities. Notwithstanding the importance of these areas the broader use of silver in chemistry, and more specifically in synthesis, has lagged behind that of other...

Levy D.E., Tang C. The Chemistry of C-Glycosides [tetrahedron Organic Chemistry Series Volume 13]

  • формат pdf
  • размер 12.57 МБ
  • добавлен 28 октября 2011 г.
Pergamon. 1995. 307 p. In recent years C-glycoside chemistry has been one of the main topics in carbohydrate chemistry, not only because of the synthetic challenges posed, but also because C-glycosides have the potential to serve as carbohydrate analogues resistant to metabolic processes. Consequently, this class of compounds is currently receiving much interest as a potential source of therapeutic agents for clinical use. This book provides a b...

Malleron J.-L., Fiaud J.-C., Legros J.-Y. Handbook of Palladium-Catalyzed Organic Reactions. Synthetic Aspects and Catalytic Cycles

Справочник
  • формат pdf
  • размер 6.36 МБ
  • добавлен 19 января 2012 г.
Academic Press 2000, 304 p. Reactions catalysed by palladium complexes Cross-Coupling of Organometallics with RX Derivatives Cross-Coupling of Organometallics with RCOX Derivatives Cross-Coupling of Siloxycyclopropanes with RX and RCOX Derivatives Cross-Coupling of Terminal Alkynes with RX Derivatives Intermolecular HECK Reaction Intramolecular HECK Reaction Intramolecular Coupling of Di(Vinyl Halides) Tandem HECK-Anion Capture Process of...

Zabicky J. (ed.) The chemistry of amides [The chemistry of functional groups]

  • формат pdf
  • размер 41.14 МБ
  • добавлен 17 августа 2011 г.
Wiley. 1970. 931 p. Molecular and electronic structure of the amide group Synthesis of amides Acid-base and complexing properties of amides Rearrangement and elimination of the amido group Photochemistry of the amido group Radiation chemistry of amides Chemistry of imidic compounds The chemistry of thioamides The chemistry of the thiohydrazide grcjup The chemistry of hydrazides Biological formation and reactions of the amido group Directing and...

Zollinger H. Diazo chemistry I. Aromatic and Heteroaromatic Compounds

  • формат djvu
  • размер 5 МБ
  • добавлен 09 марта 2011 г.
VCH. 1994. 457 p. Introduction Methods for the Preparation of Aromatic and Heteroaromatic Diazo Compounds Kinetics and Mechanism of Diazotization The Structure of Diazonium Compounds Acid-Base and Isimerization Reactions of Diazo Compounds in Water Additions of Other Nucleophiles to Arenediazonium Ions Structural and Mechanistic Aspects of Additions of Nucleophiles to Diazonium Ions Dediazoniation of Arenediazonium Ions Logic, Psychology, and Ser...