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Transition-Metal-Mediated Aromatic Ring Construction

ISBN: 978-1-118-14892-1
830 pages
August 2013
Transition-Metal-Mediated Aromatic Ring Construction (1118148924) cover image

Description

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.

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Table of Contents

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] Cycloaddition 255
Ken Tanaka and Takanori Shibata

9.1 Introduction, 255

9.2 Cobalt-Catalyzed Enantioselective [2+2+2] Cycloaddition, 256

9.3 Iridium-Catalyzed Enantioselective [2+2+2] Cycloaddition, 258

9.4 Rhodium-Catalyzed Enantioselective [2+2+2] Cycloaddition, 263

9.5 Enantioselective Synthesis of Axially Chiral Anilides and Bezamides, 275

9.6 Summary and Outlook, 278

References, 278

10 Synthesis of Helically Chiral Aromatic Compounds via [2+2+2] Cycloaddition 281
Ken Tanaka

10.1 Introduction, 281

10.2 Nonasymmetric Synthesis, 281

10.3 Diastereoselective Synthesis, 287

10.4 Enantioselective Synthesis, 290

10.5 Summary and Outlook, 296

References, 297

11 Aromatic Ring Construction from Zirconocenes and Titanocenes 299
Shi Li and Tamotsu Takahashi

11.1 Introduction, 299

11.2 Aromatic Ring Construction from Zirconocenes, 300

11.3 Aromatic Ring Construction from Titanocenes, 313

11.4 Application to Synthesis of Substituted Acenes, 315

11.5 Summary and Outlook, 317

References, 318

PART II [4+2], [3+2], AND RELATED CYCLOADDITION REACTIONS

12 [4+2] and [3+2] Cycloaddition via Metallacycles 323
Takuya Kurahashi and Seijiro Matsubara

12.1 Introduction, 323

12.2 [4+2] Cycloaddition via Elimination of Small Molecules, 326

12.3 [3+2] Cycloaddition via Elimination of Small Molecules, 332

12.4 [4+2] Cycloaddition via C C Bond Activation, 334

12.5 [4+2] Cycloaddition via C–H Bond Activation, 336

12.6 Summary and Outlook, 339

References, 339

13 Diels–Alder Reactions 341
Gerhard Hilt and Florian P¨unner

13.1 Introduction, 341

13.2 Transition-Metal-Mediated Diels–Alder Reaction/Aromatization Sequence, 342

13.3 Intramolecular Diels–Alder Reactions toward Dihydroaromatic and Aromatic Products, 349

13.4 Synthetic Applications, 350

13.5 Summary and Outlook, 352

References, 352

14 [4+2] Benzannulation of Enynes with Alkynes 355
Vladimir Gevorgyan and Olga V. Zatolochnaya

14.1 Introduction, 355

14.2 Benzannulation of Enyne with Alkyne: Gold-catalyzed Benzannulation Reaction, 356

14.3 Benzannulation of Enyne with Enyne, 358

14.4 Benzannulation of Enyne with Diyne, 365

14.5 Synthetic Applications, 371

14.6 Summary and Outlook, 376

References, 376

15 Formal [4+2] Benzannulation via Pyrylium Intermediates 379
Naoki Asao and Yoshifumi Ishikawa

15.1 Introduction, 379

15.2 Benzannulation of Pyrylium Salts, 380

15.3 Benzannulation of O-Alkynylbenzaldehydes, 380

15.4 Intramolecular [4+2] Benzannulation, 392

15.5 Application to Natural Product Synthesis, 394

15.6 Summary and Outlook, 395

References, 396

16 Utilization of 1,3-Dipolar Compounds 399
Yi-Feng Wang and Shunsuke Chiba

16.1 Introduction, 399

16.2 1,3-Dipolar Cycloaddition, 401

16.3 Five-Membered Ring Construction via Decomposition of Azides, 410

16.4 Six-Membered Ring Construction via Decomposition of Azides, 418

16.5 Summary and Outlook, 421

References, 422

17 Utilization of Transition-Metal Carbenoids 425
James Wallace Herndon, Jr.

17.1 Introduction, 425

17.2 Five-membered Aromatic Ring Construction, 426

17.3 Six-Membered Aromatic Ring Construction, 432

17.3.1 D¨otz Benzannulation Reaction, 432

17.4 Summary and Outlook, 450

References, 450

PART III ELECTROCYCLIZATION REACTIONS

18 Intramolecular Hydroarylation of Alkynes, Alkenes, and Allenes 457
Tsugio Kitamura

18.1 Introduction, 457

18.2 Intramolecular Hydroarylation, 457

18.3 Summary and Outlook, 482

References, 483

19 Intramolecular C X Bond Formation between C X or X H andAlkynes 485
Hiroaki Ohno

19.1 Introduction, 485

19.2 C X Bond Formation between C X and Alkynes, 485

19.3 C X Bond Formation between X H and Alkynes, 510

19.4 Summary and Outlook, 529

References, 529

20 Synthesis of Heterocycles via X H Bond Addition to Diynes 537
Takanori Matsuda

20.1 Introduction, 537

20.2 Synthesis of Pyrroles and Furans via Double trans Addition to 1,3-Diynes, 538

20.3 Synthesis of Pyrroles via Hydroamination of 1,4- and 1,5-Diynes, 542

20.4 Synthesis of Siloles and Germoles via Double trans Addition to 1,3-Diynes, 543

20.5 Summary and Outlook, 546

References, 546

21 Cycloaromatization via Transition Metal–Cumulenylidenes 549
Yoshiaki Nishibayashi

21.1 Introduction, 549

21.2 Cycloaromatization via Chromium–, Molybdenum–, and Tungsten–Vinylidene Complexes, 550

21.3 Cycloaromatization via Ruthenium–Vinylidene Complexes, 554

21.4 Cycloaromatization via Rhodium–Vinylidene Complexes, 558

21.5 Cycloaromatization via Gold–Vinylidene Complexes, 561

21.6 Cycloaromatization via Ruthenium–Allenylidene Complexes, 565

21.7 Summary and Outlook, 565

References, 566

PART IV COUPLING AND ADDITION REACTIONS

22 C C Bond-Forming Coupling Reactions 573
Masaki Shimizu

22.1 Introduction, 573

22.2 Cyclization, 574

22.3 Annulation, 597

22.4 Summary and Outlook, 612

References, 612

23 Synthesis of Carbazoles and Related Compounds via C E Bond-Forming Coupling Reactions 617
Koji Nakano

23.1 Introduction, 617

23.2 Synthesis of Carbazoles, 618

23.3 Synthesis of Dibenzofurans and Dibenzothiophenes, 633

23.4 Synthesis of Other Dibenzoheteroles, 637

23.5 Summary and Outlook, 642

References, 642

24 Synthesis of Aromatic Benzo-Fused Five- and Six-Membered Heterocycles via Palladium- and Copper-Catalyzed C X Bond-Forming Reactions 645
Catherine J. Ball and Michael C. Willis

24.1 Introduction, 645

24.2 C N Bond Formation, 646

24.3 C O Bond Formation, 662

24.4 C S Bond Formation, 667

24.5 Annulation of Anilines and Related Compounds with Alkynes, 671

24.6 Summary and Outlook, 676

References, 677

25 Coupling Reactions of the sp2 C H Bond with Alkynes 683
Tetsuya Satoh and Masahiro Miura

25.1 Introduction, 683

25.2 Synthesis of Arenes, 685

25.3 Synthesis of Heterocycles, 697

25.4 Summary and Outlook, 716

References, 716

PART V OTHER IMPORTANT TRANSFORMATIONS

26 Metathesis Reactions 721
Kazuhiro Yoshida

26.1 Introduction, 721

26.2 Alkene Metathesis, 722

26.3 Ene–Yne Metathesis, 736

26.4 Other Applications, 738

26.5 Summary and Outlook, 740

References and Notes, 741

27 Skeletal Rearrangement Reactions 743
Itaru Nakamura

27.1 Introduction, 743

27.2 π-Electrophilic Transition-Metal-Mediated Aromatization Reactions, 743

27.3 π-Electrophilic Transition-Metal-Mediated Aromatization Reactions, 768

27.4 Summary and Outlook, 769

References, 769

28 Dearomatization–Aromatization Sequence 773
Hiroto Yoshida

28.1 Introduction, 773

28.2 Reactions via Arynes, 774

28.3 Reactions via o-Quinodimethanes, 787

28.4 Summary and Outlook, 793

References, 794

INDEX 797

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Author Information

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.

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Reviews

“In summary, I personally have read Transition-Metal-Mediated Aromatic Ring Construction with great interest, and I believe this book is a rich source for both academic and industrial researchers.  It provides a valuable addition to the range of textbooks on organic synthesis, aromatic rings, and heterocyclic chemistry. Therefore, I warmly recommend this book and I will strongly encourage my students and colleagues to explore it.”  (Angew. Chem. Int. Ed, 1 May 2014)

 

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