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Advances in Organometallic Chemistry

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Contents

Contributors

Preface

Chapter One: The Selection of Catalysts for Metal Carbene Transformations

1. Introduction

2. Acceptor/Acceptor-Substituted Metal Carbenes

3. Acceptor-Substituted Metal Carbenes

4. Donor/Acceptor-Substituted Metal Carbenes

4.1. Alkyl/Acceptor-Substituted Metal Carbenes

4.2. Aryl/Acceptor-Substituted Metal Carbenes

4.3. Vinyl/Acceptor-Substituted Metal Carbenes

5. Donor- and Donor/Donor-Substituted Metal Carbenes

6. Summary

Acknowledgments

References

Chapter Two: Recent Advances in Asymmetric Metal-Catalyzed Carbene Transfer from Diazo Compounds Toward Molecular Complexity

1. Introduction

2. Insertion Reaction

2.1. C-H Functionalization

2.2. N-H Insertion

2.3. O-H Insertion

2.4. S-H Insertion

2.5. Si-H Insertion

2.6. B-H Insertion

3. Cycloadditions

3.1. [2C+n] Cycloaddition

3.2. [3C+n] Cycloaddition

3.3. [4C+n] Cycloaddition

3.4. [5C+n] Cycloaddition

3.5. [6C+n] Cycloaddition

3.6. Miscellaneous

4. Ylide Formation

4.1. Trapping Tactic

4.2. Cascade Reaction

5. Summary

Acknowledgments

References

Chapter Three: Copper(I)-Acetylides: Access, Structure, and Relevance in Catalysis

1. Introduction

2. Oxidative Coupling Reactions

2.1. Glaser and Hay Coupling Reactions

2.2. Oxidative Cross-Coupling Reactions

3. Cross-Coupling Reactions

3.1. Group 10-Mediated Reactions: Sonogashira Cross-Coupling

3.2. Copper-Mediated Cross-Couplings: Catalytic Castro-Stephens Reactions

3.3. Copper-Mediated Cross-Coupling of Diazo Compounds

4. Other Coupling Reactions

4.1. Carboxylation and Carboxylative Coupling Reactions

4.2. A3-Coupling Reactions

5. 1,3-Dipolar Cycloadditions

5.1. Azide-Alkyne Cycloadditions and Click Chemistry

5.2. Other Cycloaddition Reactions

6. Miscellaneous Reactions

7. Conclusions

References

Chapter Four: Phenol Derivatives: Modern Electrophiles in Cross-Coupling Reactions

1. Introduction

2. Carbon-Carbon Bond Formation

2.1. KTC-Type Coupling Reactions

2.1.1. Historical Background: Uncatalyzed Reactions and Stoichiometric Experiments

2.1.2. Ethers

2.1.3. Carbamates

2.1.4. Esters

2.1.5. Benzyl Alcohols

2.2. Negishi-Type Coupling Reactions

2.2.1. Esters

2.2.2. Ethers

2.3. Suzuki-Miyaura-Type Couplings

2.3.1. Carbamates

2.3.2. Esters

2.3.3. Ethers

2.3.4. Alcohols

2.4. Mizoroki-Heck-Type Coupling Reactions

2.4.1. Esters

2.4.2. Ethers

2.5. Stille-Type Couplings

2.6. Reactions Involving Other Organometallic Compounds: Organolithium and Organoaluminum Reagents

2.7. Miscellaneous C-C Bond-Forming Reactions

2.7.1. Reactions of Benzyl Esters with Various Nucleophiles

2.7.2. α-Arylations with Aryl Esters

2.7.3. Reductive Coupling Reactions

2.7.4. C-H/C-O Coupling Reactions

3. Carbon-Heteroatom Bond-Forming Reactions

3.1. C-N Bond Formation

3.2. C-B Bond Formation

3.3. C-Si Bond Formation

3.4. C-P Bond Formation

4. Hydrogenolysis of C-O Bonds

4.1. Ethers

4.2. Carbamates

4.3. Esters

4.4. Alcohols

5. Conclusions and Outlook

Acknowledgments

References

Chapter Five: Transition Metal Alkane-Sigma Complexes: Synthesis, Characterization, and Reactivity

1. Introduction: C-H σ-Complexes and Their Role in C-H Activation

2. Comments on Nomenclature

3. Scope of This Review

3.1. General Comments Regarding the Synthesis of σ-Alkane Complexes

3.2. In Situ Solution Synthesis and Characterization Using Photoejection of a Ligand

3.3. NMR Studies: Photogeneration Strategies

3.4. NMR Studies: Protonation of Metal Alkyls at Very Low Temperatures

3.5. Characterization of Alkane Complexes Using Preorganized Vacant Sites

3.6. Hydrogenation of Alkenes in the Solid State

4. Conclusions

Notes Added in Proof

Acknowledgments

References

Index

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