Front Cover

Advances in Organometallic Chemistry

Copyright

Dedication

Contents

Contributors

Preface

Chapter One: Group 6 Metal Fischer Carbene Complexes: Versatile Synthetic Building Blocks

1. Introduction

2. Synthesis of Group 6 Metal Carbene Complexes

3. Release of the Organic Moiety on FCCs

4. Applications of Alkyl Carbene Complexes in Organic Synthesis (and of Other Carbene Complexes in Reactions Where Only t ...

4.1. Synthesis of Acyclic Compounds

4.2. Synthesis of Three-Membered Carbocycles

4.3. Synthesis of Four-Membered Carbocycles

4.4. Synthesis of Five-Membered Carbocycles

4.5. Synthesis of Six-Membered Carbocycles

4.6. Synthesis of Seven-Membered Carbocycles

4.7. Synthesis of Heterocycles

5. Applications of Alkenyl and Aryl Carbene Complexes

5.1. Synthesis of Acyclic Compounds

5.2. Synthesis of Three-Membered Carbocycles

5.3. Synthesis of Five-Membered Carbocycles

5.4. Synthesis of Six-Membered Carbocycles

5.5. Synthesis of Seven-Membered Carbocycles

5.6. Synthesis of N-Heterocycles

5.7. Synthesis of O-Heterocycles

6. Applications of Alkynyl Carbene Complexes

6.1. Synthesis of Acyclic Compounds

6.2. Synthesis of Four-Membered Carbocycles

6.3. Synthesis of Five-Membered Carbocycles

6.4. Synthesis of Six-Membered Carbocycles

6.5. Synthesis of Seven- and Eight-Membered Carbocycles

6.6. Synthesis of Five-Membered N-Heterocycles

6.7. Synthesis of Six-Membered N-Heterocycles

6.8. Synthesis of Seven-Membered N-Heterocycles

7. Nonheteroatom-Stabilized Carbene Complexes (NHSCCs)

7.1. Synthesis of Nonheteroatom-Stabilized FCCs

7.2. Early Chemistry of NHSCCs: Cyclopropanation and Metathesis

7.3. Applications of Alkynyl NHSCCs as Stoichiometric Reagents in Organic Synthesis

7.4. Stoichiometric or Catalytic Transformations Involving NHSCCs as Intermediates Synthesized From M(CO)5L and Conjugate ...

7.4.1. Initiated by 5-exo-dig Cyclizations

7.4.2. Initiated by 5-endo-dig Cyclizations

7.4.3. Initiated by 6-Endo-dig Cyclizations

7.4.4. Initiated by Alkenylidene Formation

8. Conclusions, Summary and Outlook

Acknowledgments

References

Chapter Two: Recent Advances in Transition-Metal-Catalyzed Cross-Coupling Reactions With N-Tosylhydrazones

1. Introduction

2. Palladium-Catalyzed Coupling Reaction of N-Tosylhydrazones

2.1. Pd-Catalyzed Coupling of N-Tosylhydrazones With Aryl and Alkenyl Halides

2.2. Pd-Catalyzed Coupling of N-Tosylhydrazones With Benzyl Halides

2.3. Pd-Catalyzed Oxidative Coupling of N-Tosylhydrazones

2.4. Pd-Catalyzed Two-Component Cascade Coupling of N-Tosylhydrazones

2.5. Pd-Catalyzed Multicomponent Coupling of N-Tosylhydrazones

3. Copper-Catalyzed Coupling Reaction of N-Tosylhydrazones

3.1. Cu-Catalyzed Coupling of N-Tosylhydrazones With Alkynes

3.2. Cu-Catalyzed Coupling of N-Tosylhydrazones Involving C-H Activation

3.3. Cu-Catalyzed Oxidative Coupling Reaction of N-Tosylhydrazones

4. Rhodium-Catalyzed Coupling Reaction of N-Tosylhydrazones

5. Nickel- and Cobalt-Catalyzed Coupling Reactions of N-Tosylhydrazones

6. Catalytic Intramolecular Cyclization of N-Tosylhydrazones

7. Summary

Acknowledgments

References

Chapter Three: Oxidative Functionalization of Late Transition Metal-Carbon Bonds

1. Introduction

2. Group 7 Metals

2.1. Rhenium

2.1.1. Re-C(sp3) Bond Oxyfunctionalization

2.1.2. Re-C(sp2) Bond Oxyfunctionalization

3. Group 8 Metals

3.1. Iron

3.1.1. Oxidative C-C Coupling and Oxyfunctionalization Involving Fe-C(sp3) and Fe-C(sp2) Bonds

3.2. Ruthenium

3.2.1. Oxidative C-C Coupling Involving Ru-C(sp3) and Ru-C(sp2) Bonds

3.3. Osmium

3.3.1. Oxidative C-C Coupling Involving Os=C or Os≡C Bonds

4. Group 9 Metals

4.1. Cobalt

4.1.1. Oxidative C-C Coupling Involving Co-C(sp3) or Co-C(sp2) Bonds

4.2. Rhodium

4.2.1. Oxidative C-C Coupling Involving Rh-C(sp3) or Rh-C(sp2) Bonds

4.2.2. Oxidative C-X Coupling (X=Cl, Br, I, O, P) Involving Rh-C(sp3) Bonds

4.3. Iridium

4.3.1. Oxidative C-C Coupling Involving Ir-C(sp3), Ir-C(sp2), or Ir-C(sp) Bonds

4.3.2. Functionalization of Ir-C(sp3) and Ir=C Bonds via a Heteroatom (O, N, S) Transfer

5. Group 10 Metals

5.1. Nickel

5.1.1. Oxidative C-X Coupling (X=C, Cl, Br, I, O, P) Involving Ni-C(sp3) and Ni-C(sp2) Bonds

5.2. Palladium

5.2.1. Oxidative C-X Coupling (X=F, O, N) Involving Pd-C(sp3) Bonds

5.2.2. Functionalization of Pd(II)-C(sp3) Bonds Using O2 as Oxidant

5.2.3. Oxidative C-X Coupling (X=F, Cl, Br, O, N, C) Involving Pd-C(sp2) Bonds

5.3. Platinum

5.3.1. Oxidative C-X Coupling (X=C, Cl, I, O, N) Involving Pt-C(sp3) Bonds

5.3.2. Oxidative C-X Coupling (X=Br, O) Involving Pt(III)-C(sp3) Bonds

5.3.3. Oxidative C-X Coupling (X=C, F, Br, I) Involving Pt-C(sp2) Bonds

6. Group 11 Metals

6.1. Copper

6.1.1. Oxidative C-X Coupling (X=F, O, N) Involving Cu-C(sp2) Bonds

6.2. Silver

6.3. Gold

6.3.1. Oxidative C-X Coupling (X=Cl, Br, I, C, P) Involving Au-C(sp2) Bonds

7. Summary

Acknowledgments

References

Chapter Four: Biaryl Synthesis via C-H Bond Activation: Strategies and Methods

1. Introduction

1.1. Traditional Transition Metal-Catalyzed Cross-Coupling Reactions

1.2. Metal-Catalyzed Direct C-H Bond Arylation

2. Strategies for Metal-Catalyzed Direct C-H Arylation

2.1. Electronic Controlled Arylation Methods

2.1.1. C-H Arylation of Electron-Rich (Hetero)Arenes

2.1.2. C-H Arylation of Electron-Poor (Hetero)Arenes

2.1.2.1. Pd-Catalyzed Systems

2.1.2.2. Cu-Catalyzed Systems

2.1.2.3. Au-Catalyzed Systems

2.1.2.4. Ru-Catalyzed Systems

2.1.3. C-H Arylation of Metal-Arene π-Complexes

2.2. C-H Arylation of (Hetero)Arenes via Chelate-Assisted Metalation

2.2.1. ortho-C-H Arylation of (Hetero)Arenes Bearing a DG

2.2.1.1. DG-Assisted Pd-Catalyzed ortho-C-H Arylation

2.2.1.1.1. Pd Systems With Aryl (Pseudo)Halides

2.2.1.1.2. Pd Systems With Organometallic Species

2.2.1.1.3. Pd Systems via CDC

2.2.1.2. DG-Assisted Ru-Catalyzed ortho-C-H Arylation

2.2.1.2.1. Ru(0)-Catalyzed Systems With Organometallic Species

2.2.1.2.2. Ru(II)-Catalyzed Systems With Aryl (Pseudo)Halides

2.2.1.2.3. Ru(II)-Catalyzed Systems With Aryl Boron Reagents

2.2.1.2.4. Ru(II)-Catalyzed System via (C)DC

2.2.1.3. DG-Assisted Rh-Catalyzed ortho-C-H Arylation

2.2.1.3.1. Rh(I)/Rh(III) Systems With Organometallic Species

2.2.1.3.2. Rh(III)/Rh(I) Systems With Organometallic Species

2.2.1.3.3. Rh(I)/Rh(III) Systems via Decarbonylation

2.2.1.3.4. Rh(III)/Rh(V) Systems With Aryl Iodides

2.2.1.3.5. Rh(III) Systems via CDC

2.2.2. meta-C-H Arylation of (Hetero)Arenes Bearing a DG

2.2.2.1. meta-C-H Arylation Dictated by the Metalation Site

2.2.2.1.1. Cu-Catalyzed Systems

2.2.2.1.2. Pd-Catalyzed Systems via Nitrile-Containing Templates

2.2.2.2. meta-C-H Arylation by Hijacking the Metalation Site

2.3. C-H Arylation Methods Using a Transient DG

2.3.1. Rh-Catalyzed Systems via Transesterification

2.3.2. Pd-Catalyzed Systems via Imine Formation

3. Conclusions and Outlook

Acknowledgments

References

Chapter Five: Carbon-Nitrogen Bond Formation Through Cross-Dehydrogenative Coupling Reactions

1. Introduction

1.1. The Importance of Nitrogen-Containing Compounds

1.2. Amine Synthesis: From Classical to State-of-the-Art Methods

1.3. Scope of the Review

2. Direct Oxidative Amination

2.1. Intramolecular C(sp2)-N Bond Formation

2.1.1. C-H Bonds of (Hetero)arenes

2.1.2. C-H Bonds of Imines and Alkenes

2.2. Intramolecular C(sp3)-N Bond Formation

2.3. Intermolecular CDCs

2.3.1. Intermolecular C(sp2)-N Bond Formation

2.3.2. Intermolecular C(sp3)-N Bond Formation

2.4. Direct Oxidative Amination With Insertion

2.5. Electrochemical CDCs

3. Conclusions and Outlook

Acknowledgments

References

Index

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