Title Details

Lutz Ackermann is Professor of Chemistry at Georg-August-University Göttingen, Germany. He obtained his Ph.D. under the supervision of Prof. Dr. A. Fürstner at the Max-Planck-Institut für Kohlenforschung in Mülheim/Ruhr, Germany, in 2001. He then was a postdoctoral fellow with Prof. R.G. Bergman at the University of California (Berkeley, USA), before initiating his independent career in 2003 at Ludwig-Maximilians-University in Munich, Germany. In 2007, he was promoted to full professor at the Georg August-University Göttingen. His research is focused on the development of novel concepts for sustainable catalysis, with a topical focus on C-H activations. He was awarded, among others, the Gottfried-Wilhelm-Leibniz Prize (2017), an ERC Grant (2012), the BASF Lecture at UC Berkeley (2014), and held visiting professorships in Milano, Perugia, Pavia (Italy), Wisconsin, Madison (USA), and Osaka (Japan). He is the editor of the book "Modern Arylation Methods" (Wiley-VCH) and has co-authored more than 8 book chapters and 240 referred journal publications.

T. Brent Gunnoe is the Commonwealth Professor of Chemistry at the University of Virginia, USA, since 2008. He received his Ph.D. from the University of North Carolina (USA) in 1997 under the director of Prof. J. Templeton and did postdoctoral work at the University of Virginia from 1997 to 1999. He began his independent career as an assistant professor at North Carolina State University in 1999. He was the recipient of a NSF CAREER Award, an Alfred P. Sloan Research Fellowship and the LeRoy and Elva Martin Award for Teaching Excellence. He currently serves as associate editor for "ACS Catalysis". From 2009 until 2015 he was the Director of the Center for Catalytic Hydrocarbon Functionalization (CCHF), which was an Energy Frontier Research Center funded by the United States Department of Energy. Currently, he leads the University of Virginia effort within MAXNET Energy, a consortium from the Max Planck Society that is focused on the develop and understanding of catalytic processes for energy production and use. He is co-inventor on three patents, co-author of four book chapters and more than 135 referred journal publications, and he has delivered over 100 invited lectures that are focused on fundamental aspects of catalyst technologies applied to the development of new energy resources as well as improved processes for the petrochemical industry and fine chemical synthesis.

Laurel Goj Habgood is an Associate Professor of Chemistry at Rollins College (USA). She obtained her Ph.D. from Duke University (USA) under the direction of Prof. R. Widenhoefer in 2004. She completed postdoctoral research in the group of Prof. T. B. Gunnoe at North Carolina University (USA) from 2004 to 2006 and a sabbatical project with the group at the University of Virginia (USA) in 2012. In 2006 she started her independent career at Rollins College. Her research with undergraduates utilizes metal-NHC complexes as catalysts for organic transformations. She was awarded the endowed D.J. and J.M. Cram Chair of Chemistry in 2014 and currently serves as chair of the Department of Chemistry at Rollins College.

List of Contributors xi

Introduction and Preface 1

Laurel G. Habgood, Lutz Ackermann, and T. Brent Gunnoe

References 3

1 Functionalization of Heteroaromatic Substrates using Groups 9 and 10 Catalysts 5
Pedro Villuendas, Sara Ruiz, and Esteban P. Urriolabeitia

1.1 Introduction 5

1.2 Thiophenes, furans, and Related Heterocycles 8

1.3 Pyrroles, Indoles, Pyridines, and Imidazopyridines 21

1.4 Azoles and Other Miscellaneous Heterocycles 31

1.5 Summary 39

References 40

2 Ruthenium Catalysts for the Alkylation of Functionalized Arenes and Heteroaromatic Substrates via Hydroarylation 49
David J. Burns, Sergei I. Kozhushkov, and Lutz Ackermann

2.1 Introduction 49

2.2 Alkylation by Ruthenium(0) Catalysts via Oxidative-Addition C–H Activation 50

2.2.1 Alkylation by Ruthenium(II) Catalysts via Carboxylate-Assisted C–H Activation 63

2.3 Summary and Conclusions 70

Abbreviations 71

References 71

3 Alkylation of ArenesWithout Chelation Assistance: Transition Metal Catalysts with d6 Electron Configurations 83
Bradley A. McKeown, Laurel Goj Habgood, Thomas R. Cundari, and T. Brent Gunnoe

3.1 Transition Metal-Mediated Arene Alkylation: Overview 83

3.2 Octahedral d6 Transition Metal Catalysts for Olefin Hydroarylation: Scorpionate Supported Ru(II) Catalysts 85

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 90

3.2.2 Ethylene Hydrophenylation Catalyzed by Cationic Ru(II) Complexes Ligated by Poly(pyrazolyl)alkanes 93

3.3 Olefin Hydroarylation Catalyzed by Octahedral d6 Ir(III) Supported by the Acetylacetonate Ligand 95

3.3.1 Mechanism of Catalytic Olefin Hydrophenylation using Ir(III) Supported by the Acetylacetonate Ligand 96

3.3.2 Other d6 Ir(III) Catalysts 98

3.4 Summary: Comparison of Ru(II) and Ir(III) Catalysts for Olefin Hydroarylation 99

3.5 Future Outlook: Extension of Olefin Hydroarylation using Hydrocarbons to Earth Abundant Metals 100

References 102

4 Hydroarylation of Olefins with Complexes Bearing d8 Metal Centers 107
Benjamin A. Suslick and T. Don Tilley

4.1 Introduction 107

4.2 PtII Catalyzed Hydroarylation 109

4.2.1 PtII Hydroarylation Catalysts Bearing Anionic Bidentate (NN) Ligands 109

4.2.2 PtII Hydroarylation Catalysts Bearing Neutral Bidentate (NN) Ligands 114

4.2.3 PtII Hydroarylation Catalysts Supported by Nonnitrogen-based Ligands 119

4.2.4 Summary of PtII Catalyzed Hydroarylations 123

4.3 RhI-Catalyzed Hydroarylation 124

4.3.1 Reactions of Unfunctionalized Arenes with RhI Complexes Proceeding via Hydroarylation-LikeMechanisms 124

4.3.2 Directed ortho-Hydroarylation Catalyzed by RhI Complexes 126

4.3.3 RhI-Catalyzed Hydroarylation with Fluorinated Arenes 142

4.3.4 Summary of RhI-Catalyzed Hydroarylation 142

4.4 Directed ortho-Hydroarylation Catalyzed by IrI Complexes 144

4.5 Hydroarylation with Ni0 Complexes via NiII Intermediates 152

4.6 Formal Hydroarylation Reactions with PdII Catalysts via Heck-Like Mechanisms 155

4.6.1 Formate-Assisted PdII Catalyzed Hydroarylation 155

4.6.2 Oxidatively Coupled PdII-Catalyzed Hydroarylation with Aryltin and Arylboronic Ester Substrates 160

4.6.3 Summary of PdII-Catalyzed Formal Hydroarylation Reactions 163

4.7 Conclusions 166

References 166

5 Hydroarylation of C–C Multiple Bonds Using Nickel Catalysts 175
Yoshiaki Nakao

5.1 Introduction 175

5.2 Hydroarylation of Alkynes 175

5.3 Hydroheteroarylation of Alkynes 179

5.3.1 Hydroheteroarylation of Alkynes with five-Membered Heteroarenes 179

5.3.2 Hydroheteroarylation of Alkynes with Azine-N-oxides 182

5.3.3 Hydroheteroarylation of Alkynes with Azines 182

5.4 Hydroarylation of Alkenes 184

5.5 Hydroheteroarylation of Alkenes 185

5.5.1 Hydroheteroarylation of Alkenes with five-Membered Heteroarenes 185

5.5.2 Hydroheteroarylation of Alkenes with Azines 188

5.6 Summary and Outlook 189

References 190

6 Hydroarylation of Alkynes and Alkenes using Group 7–9 First-Row Transition Metal Catalysts 193
Naohiko Yoshikai

6.1 Introduction 193

6.2 Hydroarylation of Alkynes and Alkenes using Cobalt Catalysts 194

6.2.1 Hydroarylation of Alkynes using Low-Valent Cobalt Catalysts 194

6.2.2 Hydroarylation of Alkenes using Low-Valent Cobalt Catalysts 199

6.2.3 Hydroarylation of Alkynes and Alkenes using Cp*CoIII Catalysts 206

6.3 Hydroarylation of Alkynes and Alkenes using Iron Catalysts 208

6.3.1 Hydroarylation of Alkynes and Alkenes using Low-Valent Iron Catalysts 208

6.3.2 Hydroarylation of Alkenes using Lewis Acidic Iron Catalysts 208

6.4 Hydroarylation of Alkynes using Low-Valent Manganese Catalyst 209

6.5 Conclusions 211

6.6 Abbreviations 211

References 212

7 Hydroarylation of Alkynes using Cu, Ag, and Au Catalysts 217
Mariia S. Kirillova, Fedor M.Miloserdov, and AntonioM. Echavarren

7.1 Introduction 217

7.2 Intramolecular Hydroarylation of Alkynes 218

7.2.1 Alkyne Hydroarylation with Electron-Rich Arenes 218

7.2.1.1 Alkyne Hydroarylation with Aniline Derivatives 218

7.2.1.2 Alkyne Hydroarylation with Phenols and Phenol Ether Derivatives 225

7.2.2 Alkyne Hydroarylation with Other Arenes 231

7.2.3 Alkyne Hydroarylation with Indoles 237

7.2.3.1 Alkenylation of Indoles at the 2-Position 239

7.2.3.2 Alkenylation of Indoles at the 3-position 242

7.2.3.3 Spirocyclizations 244

7.2.3.4 More Complex Transformations Featuring a Hydroarylation of Alkynes 246

7.2.4 Alkyne Hydroarylation with Pyrroles 258

7.2.5 Alkyne Hydroarylation with Furans and Benzofurans 263

7.2.5.1 Alkenylation at the 2-Position of Furan 264

7.2.5.2 Alkenylation at the 3-Position of Furan 265

7.2.5.3 More Complex Transformations Featuring Hydroarylation of Alkynes 265

7.2.5.4 The Furan–Yne Cycloisomerization to Phenols 270

7.2.6 Alkyne Hydroarylation withThiophenes and Benzothiophenes 276

7.3 Intermolecular Hydroarylation of Alkynes 277

7.3.1 Intermolecular Hydroarylation of Alkynes with Arenes 277

7.3.2 Intermolecular Hydroarylation of Alkynes with Heteroarenes 278

7.3.2.1 N-Heterocycles 279

7.3.2.2 O-Heterocycles 282

7.4 Metal-Supported Catalysts and Their Applications in Hydroarylation of Alkynes 284

7.5 Hydroarylation of Alkynes in Total Synthesis 288

References 291

8 Catalytic Alkyne Hydroarylation Using Arylboron Reagents, Aryl Halides, and Congeners 305
Yoshihiko Yamamoto

8.1 Introduction 305

8.2 Catalyzed Alkyne Hydroarylations Using Arylboron and Arylsilicon Reagents 307

8.2.1 Rhodium-Catalyzed Reactions 308

8.2.2 Palladium-Catalyzed Reactions 315

8.2.3 Reactions Catalyzed by First Row Transition Metals 321

8.3 Catalyzed Alkyne Hydroarylations Using Aryl Halides and Arenediazonium Compounds 326

8.3.1 Intermolecular Reductive Heck Reactions 327

8.3.2 Intramolecular Reductive Heck Reactions 333

8.4 Synthetic Applications of Alkyne Hyaroarylations Using Arylboron Reagents and Aryl Halides 336

8.4.1 Sequential Processes Involving Alkyne Hydroarylations Using Arylboron Reagents and Aryl Halides 336

8.4.1.1 Synthesis of Oxygen Heterocycles 336

8.4.1.2 Synthesis of Nitrogen and Phosphorous Heterocycles 341

8.4.1.3 Synthesis of Carbocycles 346

8.4.2 Synthesis of Bioactive Compounds and Natural Products via Alkyne Hydroarylations Using Arylboron Reagents and Aryl Halides 348

8.5 Summary 352

References 354

9 Transition Metal-Catalyzed Hydroarylation of Allenes 361
Ross A.Widenhoefer

9.1 Introduction 361

9.2 Intramolecular Hydroarylation 362

9.2.1 Indoles as Nucleophiles 362

9.2.1.1 6-exo-Hydroarylation 362

9.2.1.2 5-exo-Hydroarylation 363

9.2.1.3 6-endo-Hydroarylation 364

9.2.1.4 5-endo-Hydroarylation 365

9.2.1.5 Less Common Modes of Ring Closure 367

9.2.2 Other Nucleophiles 368

9.2.2.1 6-exo-Hydroarylation 368

9.2.2.2 6-endo-Hydroarylation 373

9.2.2.3 Less Common Modes of Ring Closure 376

9.3 Intermolecular Hydroarylation 378

9.3.1 Indoles as Nucleophiles 378

9.3.1.1 Monoaddition Processes 378

9.3.1.2 Tandem Addition Processes 378

9.3.2 Furans as Nucleophiles 379

9.3.3 Alkoxy Benzenes as Nucleophiles 381

9.3.4 Alkyl Benzenes as Nucleophiles 383

9.4 Enantioselective Hydroarylation 384

9.4.1 Intramolecular Hydroarylation 384

9.4.2 Intermolecular Hydroarylation 384

9.5 Summary and Outlook 385

References 386

Index 389