Cover

Title Page

Copyright

Contents

Introduction and Preface

References

Chapter 1 Functionalization of Heteroaromatic Substrates using Groups 9 and 10 Catalysts

1.1 Introduction

1.2 Thiophenes, furans, and Related Heterocycles

1.3 Pyrroles, Indoles, Pyridines, and Imidazopyridines

1.4 Azoles and Other Miscellaneous Heterocycles

1.5 Summary

References

Chapter 2 Ruthenium Catalysts for the Alkylation of Functionalized Arenes and Heteroaromatic Substrates via Hydroarylation

2.1 Introduction

2.2 Alkylation by Ruthenium(0) Catalysts via Oxidative-Addition C-H Activation

2.2.1 Alkylation by Ruthenium(II) Catalysts via Carboxylate-Assisted C-H Activation

2.3 Summary and Conclusions

Abbreviations

References

Chapter 3 Alkylation of Arenes Without Chelation Assistance: Transition Metal Catalysts with d6 Electron Configurations

3.1 Transition Metal-Mediated Arene Alkylation: Overview

3.2 Octahedral d6 Transition Metal Catalysts for Olefin Hydroarylation: Scorpionate Supported Ru(II) Catalysts

3.2.1 Structure–Activity Relationships with TpRu(L)(NCMe)Ph: Examination of Elementary Steps and Catalytic Hydrophenylation of Ethylene as a Function of Ligand L

3.2.2 Ethylene Hydrophenylation Catalyzed by Cationic Ru(II) Complexes Ligated by Poly(pyrazolyl)alkanes

3.3 Olefin Hydroarylation Catalyzed by Octahedral d6 Ir(III) Supported by the Acetylacetonate Ligand

3.3.1 Mechanism of Catalytic Olefin Hydrophenylation using Ir(III) Supported by the Acetylacetonate Ligand

3.3.2 Other d6 Ir(III) Catalysts

3.4 Summary: Comparison of Ru(II) and Ir(III) Catalysts for Olefin Hydroarylation

3.5 Future Outlook: Extension of Olefin Hydroarylation using Hydrocarbons to Earth Abundant Metals

References

Chapter 4 Hydroarylation of Olefins with Complexes Bearing d8 Metal Centers

4.1 Introduction

4.2 PtII Catalyzed Hydroarylation

4.2.1 PtII Hydroarylation Catalysts Bearing Anionic Bidentate (NN) Ligands

4.2.2 PtII Hydroarylation Catalysts Bearing Neutral Bidentate (NN) Ligands

4.2.3 PtII Hydroarylation Catalysts Supported by Nonnitrogen-based Ligands

4.2.4 Summary of PtII Catalyzed Hydroarylations

4.3 RhI-Catalyzed Hydroarylation

4.3.1 Reactions of Unfunctionalized Arenes with RhI Complexes Proceeding via Hydroarylation-Like Mechanisms

4.3.2 Directed ortho-Hydroarylation Catalyzed by RhI Complexes

4.3.3 RhI-Catalyzed Hydroarylation with Fluorinated Arenes

4.3.4 Summary of RhI-Catalyzed Hydroarylation

4.4 Directed ortho-Hydroarylation Catalyzed by IrI Complexes

4.5 Hydroarylation with Ni0 Complexes via NiII Intermediates

4.6 Formal Hydroarylation Reactions with PdII Catalysts via Heck-Like Mechanisms

4.6.1 Formate-Assisted PdII Catalyzed Hydroarylation

4.6.2 Oxidatively Coupled PdII-Catalyzed Hydroarylation with Aryltin and Arylboronic Ester Substrates

4.6.3 Summary of PdII-Catalyzed Formal Hydroarylation Reactions

4.7 Conclusions

References

Chapter 5 Hydroarylation of C-C Multiple Bonds Using Nickel Catalysts

5.1 Introduction

5.2 Hydroarylation of Alkynes

5.3 Hydroheteroarylation of Alkynes

5.3.1 Hydroheteroarylation of Alkynes with five-Membered Heteroarenes

5.3.2 Hydroheteroarylation of Alkynes with Azine-N-oxides

5.3.3 Hydroheteroarylation of Alkynes with Azines

5.4 Hydroarylation of Alkenes

5.5 Hydroheteroarylation of Alkenes

5.5.1 Hydroheteroarylation of Alkenes with five-Membered Heteroarenes

5.5.2 Hydroheteroarylation of Alkenes with Azines

5.6 Summary and Outlook

References

Chapter 6 Hydroarylation of Alkynes and Alkenes using Group 7–9 First-Row Transition Metal Catalysts

6.1 Introduction

6.2 Hydroarylation of Alkynes and Alkenes using Cobalt Catalysts

6.2.1 Hydroarylation of Alkynes using Low-Valent Cobalt Catalysts

6.2.2 Hydroarylation of Alkenes using Low-Valent Cobalt Catalysts

6.2.3 Hydroarylation of Alkynes and Alkenes using Cp*CoIII Catalysts

6.3 Hydroarylation of Alkynes and Alkenes using Iron Catalysts

6.3.1 Hydroarylation of Alkynes and Alkenes using Low-Valent Iron Catalysts

6.3.2 Hydroarylation of Alkenes using Lewis Acidic Iron Catalysts

6.4 Hydroarylation of Alkynes using Low-Valent Manganese Catalyst

6.5 Conclusions

6.6 Abbreviations

References

Chapter 7 Hydroarylation of Alkynes using Cu, Ag, and Au Catalysts

7.1 Introduction

7.2 Intramolecular Hydroarylation of Alkynes

7.2.1 Alkyne Hydroarylation with Electron-Rich Arenes

7.2.1.1 Alkyne Hydroarylation with Aniline Derivatives

7.2.1.2 Alkyne Hydroarylation with Phenols and Phenol Ether Derivatives

7.2.2 Alkyne Hydroarylation with Other Arenes

7.2.3 Alkyne Hydroarylation with Indoles

7.2.3.1 Alkenylation of Indoles at the 2-Position

7.2.3.2 Alkenylation of Indoles at the 3-position

7.2.3.3 Spirocyclizations

7.2.3.4 More Complex Transformations Featuring a Hydroarylation of Alkynes

7.2.4 Alkyne Hydroarylation with Pyrroles

7.2.5 Alkyne Hydroarylation with Furans and Benzofurans

7.2.5.1 Alkenylation at the 2-Position of Furan

7.2.5.2 Alkenylation at the 3-Position of Furan

7.2.5.3 More Complex Transformations Featuring Hydroarylation of Alkynes

7.2.5.4 The Furan–Yne Cycloisomerization to Phenols

7.2.6 Alkyne Hydroarylation with Thiophenes and Benzothiophenes

7.3 Intermolecular Hydroarylation of Alkynes

7.3.1 Intermolecular Hydroarylation of Alkynes with Arenes

7.3.2 Intermolecular Hydroarylation of Alkynes with Heteroarenes

7.3.2.1 N-Heterocycles

7.3.2.2 O-Heterocycles

7.4 Metal-Supported Catalysts and Their Applications in Hydroarylation of Alkynes

7.5 Hydroarylation of Alkynes in Total Synthesis

References

Chapter 8 Catalytic Alkyne Hydroarylation Using Arylboron Reagents, Aryl Halides, and Congeners

8.1 Introduction

8.2 Catalyzed Alkyne Hydroarylations Using Arylboron and Arylsilicon Reagents

8.2.1 Rhodium-Catalyzed Reactions

8.2.2 Palladium-Catalyzed Reactions

8.2.3 Reactions Catalyzed by First Row Transition Metals

8.3 Catalyzed Alkyne Hydroarylations Using Aryl Halides and Arenediazonium Compounds

8.3.1 Intermolecular Reductive Heck Reactions

8.3.2 Intramolecular Reductive Heck Reactions

8.4 Synthetic Applications of Alkyne Hyaroarylations Using Arylboron Reagents and Aryl Halides

8.4.1 Sequential Processes Involving Alkyne Hydroarylations Using Arylboron Reagents and Aryl Halides

8.4.1.1 Synthesis of Oxygen Heterocycles

8.4.1.2 Synthesis of Nitrogen and Phosphorous Heterocycles

8.4.1.3 Synthesis of Carbocycles

8.4.2 Synthesis of Bioactive Compounds and Natural Products via Alkyne Hydroarylations Using Arylboron Reagents and Aryl Halides

8.5 Summary

References

Chapter 9 Transition Metal-Catalyzed Hydroarylation of Allenes

9.1 Introduction

9.2 Intramolecular Hydroarylation

9.2.1 Indoles as Nucleophiles

9.2.1.1 6-exo-Hydroarylation

9.2.1.2 5-exo-Hydroarylation

9.2.1.3 6-endo-Hydroarylation

9.2.1.4 5-endo-Hydroarylation

9.2.1.5 Less Common Modes of Ring Closure

9.2.2 Other Nucleophiles

9.2.2.1 6-exo-Hydroarylation

9.2.2.2 6-endo-Hydroarylation

9.2.2.3 Less Common Modes of Ring Closure

9.3 Intermolecular Hydroarylation

9.3.1 Indoles as Nucleophiles

9.3.1.1 Monoaddition Processes

9.3.1.2 Tandem Addition Processes

9.3.2 Furans as Nucleophiles

9.3.3 Alkoxy Benzenes as Nucleophiles

9.3.4 Alkyl Benzenes as Nucleophiles

9.4 Enantioselective Hydroarylation

9.4.1 Intramolecular Hydroarylation

9.4.2 Intermolecular Hydroarylation

9.5 Summary and Outlook

References

Index

EULA