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.
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
About the Author :
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.
Review :
“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)
