State-of-the-science methods, synthetic routes, and
strategies to construct aromatic rings

The development of new reactions for the synthesis of aromatic
compounds is a highly active research area in organic synthesis,
providing new functional organic materials, functional reagents,
and biologically active compounds. Recently, significant advances
in transition-metal-mediated reactions have enabled the efficient
and practical construction of new aromatic rings with useful
properties and applications. This book draws together and reviews
all the latest discoveries and methods in transition-metal-mediated
reactions, offering readers promising new routes to design and
construct complex aromatic compounds.

Integrating metal catalysis with aromatic compound synthesis,
Transition-Metal-Mediated Aromatic Ring Construction offers
a practical guide to the methods, synthetic routes, and strategies
for constructing aromatic compounds. The book's five parts
examine:

* [2+2+2], [2+2+1], and related cycloaddition reactions

* [4+2], [3+2], and related cycloaddition reactions

* Electrocyclization reactions

* Coupling and addition reactions

* Other important transformations, including methathesis
reactions and skeletal rearrangement reactions

Edited by Ken Tanaka, an internationally recognized expert in
the field of transition-metal catalysis, the book features authors
who are leading pioneers and researchers in synthetic reactions.
Their contributions reflect a thorough review and analysis of the
literature as well as their own firsthand laboratory experience
developing new aromatic compounds.

All chapters end with a summary and outlook, setting forth new
avenues of research and forecasting new discoveries. There are also
references at the end of each chapter, guiding readers to important
original research reports and reviews.

In summary, Transition-Metal-Mediated Aromatic Ring
Construction offers synthetic chemists a promising new avenue
for the development of important new aromatic compounds with a
broad range of applications.

KEN TANAKA is Professor in the Department of Applied Chemistry at the Tokyo University of Agriculture and Technology. Previously, he worked for the Mitsubishi Chemical Corporation in organic process research. Dr. Tanaka has published more than 100 scientific papers concerning transition-metal catalysis.

State-of-the-science methods, synthetic routes, and strategies to construct aromatic rings

The development of new reactions for the synthesis of aromatic compounds is a highly active research area in organic synthesis, providing new functional organic materials, functional reagents, and biologically active compounds. Recently, significant advances in transition-metal-mediated reactions have enabled the efficient and practical construction of new aromatic rings with useful properties and applications. This book draws together and reviews all the latest discoveries and methods in transition-metal-mediated reactions, offering readers promising new routes to design and construct complex aromatic compounds.

Integrating metal catalysis with aromatic compound synthesis, Transition-Metal-Mediated Aromatic Ring Construction offers a practical guide to the methods, synthetic routes, and strategies for constructing aromatic compounds. The book's five parts examine:

• [2+2+2], [2+2+1], and related cycloaddition reactions
• [4+2], [3+2], and related cycloaddition reactions
• Electrocyclization reactions
• Coupling and addition reactions
• Other important transformations, including methathesis reactions and skeletal rearrangement reactions

Edited by Ken Tanaka, an internationally recognized expert in the field of transition-metal catalysis, the book features authors who are leading pioneers and researchers in synthetic reactions. Their contributions reflect a thorough review and analysis of the literature as well as their own firsthand laboratory experience developing new aromatic compounds.

All chapters end with a summary and outlook, setting forth new avenues of research and forecasting new discoveries. There are also references at the end of each chapter, guiding readers to important original research reports and reviews.

In summary, Transition-Metal-Mediated Aromatic Ring Construction offers synthetic chemists a promising new avenue for the development of important new aromatic compounds with a broad range of applications.

CONTRIBUTORS xvii

PREFACE xxi

PART I [2 + 2 + 2] AND RELATED CYCLOADDITION REACTIONS

1 Cobalt-Mediated [2+2+2] Cycloaddition 3 Vincent Gandon

1.1 Introduction, 3

1.2 Synthesis of Benzenes, 4

1.3 Synthesis of Heterocycles, 15

1.4 Mechanistic Aspects, 24

1.5 Synthetic Applications, 26

1.6 Summary and Outlook, 30

References, 31

2 Nickel-Mediated [2+2+2] Cycloaddition 37 Puneet Kumar and Janis Louie

2.1 Introduction, 37

2.2 Synthesis of Benzenes, 37

2.3 Cycloaddition of Alkynes and Nitriles, 45

2.4 Cycloaddition of Alkynes and Imines, 49

2.5 Cycloaddition of Alkynes and Carbon Dioxide, 50

2.6 Cycloaddition of Alkynes and Isocyanates, 51

2.7 Cycloaddition of Alkynes and Carbodiimide, 54

2.8 Cycloaddition of Diynes and Ketenes, 54

2.9 Cycloaddition of Arynes, 55

2.10 Mechanism, 58

2.11 Summary and Outlook, 69

References, 69

3 Ruthenium-Mediated [2+2+2] Cycloaddition 71 Yoshihiko Yamamoto

3.1 Introduction, 71

3.2 Synthesis of Benzenes, 72

3.3 Synthesis of Heterocycles, 92

3.4 Mechanism of Ruthenium-Catalyzed [2+2+2] Cycloadditions, 101

3.5 Synthetic Applications, 111

3.6 Summary and Outlook, 119

References, 120

4 Rhodium-Mediated [2+2+2] Cycloaddition 127 Ken Tanaka

4.1 Introduction, 127

4.2 Synthesis of Benzenes, 128

4.3 Synthesis of Pyridines, 147

4.4 Synthesis of Pyridones and Related Heterocycles, 153

4.5 Summary and Outlook, 157

References, 158

5 Iridium-Mediated [2+2+2] Cycloaddition 161 Ryo Takeuchi

5.1 Introduction, 161

5.2 Synthesis of Benzene Derivatives, 162

5.3 Synthesis of Heterocyclic Compounds, 169

5.4 Mechanistic Aspects, 175

5.5 Summary and Outlook, 179

References, 179

6 [2+2+2] and Related Cycloadditions Mediated by Other Transition Metals 183 Ken Tanaka and Yu Shibata

6.1 Introduction, 183

6.2 Palladium-Catalyzed [2+2+2] and [2+2+1] Cycloadditions, 183

6.3 Iron-Catalyzed [2+2+2] Cycloaddition, 196

6.4 Manganese-Catalyzed [2+2+2] Cycloaddition, 199

6.5 Rhenium-Catalyzed [2+2+2], [2+1+2+1], and [2+2+1+1] Cycloadditions, 200

6.6 Other Transition-Metal-Catalyzed [2+2+2] Cycloaddition, 202

6.7 Summary and Outlook, 203

References, 203

7 Application to the Synthesis of Natural Products 207 Bernhard Witulski and Julien Grand

7.1 Introduction, 207

7.2 Construction of Benzene Rings, 209

7.3 Construction of a Heterocyclic Ring, 226

7.4 Miscellaneous, 231

7.5 Summary and Outlook, 238

References, 239

8 Synthesis of Planar Chiral Aromatic Compounds via [2+2+2] Cycloaddition 243 Takanori Shibata and Ken Tanaka

8.1 Introduction, 243

8.2 Cobalt-Catalyzed [2+2+2] Cycloaddition, 246

8.3 Rhodium-Catalyzed [2+2+2] Cycloaddition, 247

8.4 Enantioselective [2+2+2] Cycloaddition, 249

8.5 Summary and Outlook, 252

References, 252

9 Synthesis of Axially Chiral Aromatic Compounds via [2+2+2] C…