The development of catalytic versions of cascade reactions has become one of the most active and burgeoning reaction areas in organic synthesis. Covering both organocatalysis and transition–metal catalysis for these reactions, Catalytic Cascade Reactions illustrates the versatility and application of cascade reactions for synthesizing valuable compounds, such as drugs and natural products. Highlighting catalytic versus non–catalytic reactions, an important shift in academic and industry practice, the text brings chemists and the organic synthesis community up to speed on the many recent advances in the field. INDICE: Contributors xi Preface xiii 1 Amine–Catalyzed Cascade Reactions 1 Aiguo Song and Wei Wang 1.1 Introduction, 2 1.2 Enamine–Activated Cascade Reactions, 3 1.2.1 Enamine–Enamine Cascades, 3 1.2.2 Enamine–Iminium Cascades, 8 1.2.3 Enamine Catalysis Cyclization, 19 1.3 Iminium–Initiated Cascade Reactions, 21 1.3.1 Design of Iminium–Enamine Cascade Reactions, 21 1.3.2 Iminium–Activated Diels–Alder Reactions, 22 1.3.3 Iminium–Activated Sequential [4 + 2] Reactions, 24 1.3.4 Iminium–Activated [3 + 2] Reactions, 25 1.3.5 Iminium–Activated Sequential [3 + 2] Reactions, 27 1.3.6 Iminium–Activated [2 + 1] Reactions, 30 1.3.7 Iminium–Activated Multicomponent Reactions, 35 1.3.8 Iminium–Activated [3 + 3] Reactions, 37 1.4 Cycle–Specific Catalysis Cascades, 42 1.5 Other Strategies, 45 1.6 Summary and Outlook, 46 References, 46 2 Brønsted Acid–Catalyzed Cascade Reactions 53 Jun Jiang and Liu–Zhu Gong 2.1 Introduction, 54 2.2 Protonic Acid–Catalyzed Cascade Reactions, 55 2.2.1 Mannich Reaction, 55 2.2.2 Pictect–Spengler Reaction, 56 2.2.3 Biginelli Reaction, 58 2.2.4 Povarov Reaction, 59 2.2.5 Reduction Reaction, 60 2.2.6 1,3–Dipolar Cycloaddition, 61 2.2.7 Darzen Reaction, 65 2.2.8 Acyclic Aminal and Hemiaminal Synthesis, 66 2.2.9 Rearrangement Reaction, 67 2.2.10 a,b–Unsaturated Imine–Involved Cyclization Reaction, 69 2.2.11 Alkylation Reaction, 69 2.2.12 Desymmetrization Reaction, 70 2.2.13 Halocyclization, 71 2.2.14 Redox Reaction, 72 2.2.15 Isocyanide–Involved Multicomponent Reaction, 73 2.2.16 Other Protonic Acid–Catalyzed Cascade Reactions, 75 2.3 Chiral Thiourea (Urea)–Catalyzed Cascade Reactions, 75 2.3.1 Neutral Activation, 76 2.3.2 Anion–Binding Catalysis, 99 2.4 Brønsted Acid and Transition Metal Cooperatively Catalyzed Cascade Reactions, 104 2.4.1 Dual Catalysis, 105 2.4.2 Cascade Catalysis, 108 2.5 Conclusions, 116 References, 117 3 Application of Organocatalytic Cascade Reactions in Natural Product Synthesis and Drug Discovery 123 Yao Wang and Peng–Fei Xu 3.1 Introduction, 123 3.2 Amine–Catalyzed Cascade Reactions in Natural Product Synthesis, 125 3.2.1 Iminium–Ion–Catalyzed Cascade Reactions in Natural Product Synthesis, 125 3.2.2 Cycle–Specific Cascade Catalysis in Natural Product Synthesis, 129 3.3 Brønsted Acid–Catalyzed Cascade Reactions in Natural Product Synthesis, 137 3.4 Bifunctional Base/Brønsted Acid–Catalyzed Cascade Reactions in Natural Product Synthesis, 139 3.5 Summary and Outlook, 140 References, 142 4 Gold–Catalyzed Cascade Reactions 145 Yanzhao Wang and Liming Zhang 4.1 Introduction, 145 4.2 Cascade Reactions of Alkynes, 147 4.2.1 Cascade Reactions of Enynes, 147 4.2.2 Cascade Reactions of Propargyl Carboxylates, 156 4.2.3 Cascade Reactions of ortho–Substituted Arylalkynes, 161 4.2.4 Cascade Reactions of Other Alkynes, 165 4.3 Cascade Reactions of Allenes, 170 4.4 Cascade Reactions of Alkenes and Cyclopropenes, 173 4.5 Closing Remarks, 174 References, 174 5 Cascade Reactions Catalyzed by Ruthenium, Iron, Iridium, Rhodium, and Copper 179 Yanguang Wang and Ping Lu 5.1 Introduction, 179 5.2 Ruthenium–Catalyzed Transformations, 180 5.3 Iron–Catalyzed Transformations, 185 5.4 Iridium–Catalyzed Transformations, 191 5.5 Rhodium–Catalyzed Transformations, 194 5.6 Copper–Catalyzed Transformations, 202 5.7 Miscellaneous Catalytic Reactions, 215 5.8 Summary, 219 References, 219 6 Palladium–Catalyzed Cascade Reactions of Alkenes, Alkynes, and Allenes 225 Hongyin Gao and Junliang Zhang 6.1 Introduction, 226 6.2 Cascade Reactions Involving Alkenes, 226 6.2.1 Double Mizoroki–Heck Reaction Cascade, 226 6.2.2 Cascade Heck Reaction/C–H Activation, 227 6.2.3 Cascade Heck Reaction/Reduction/Cyclization, 230 6.2.4 Cascade Heck Reaction/Carbonylation, 231 6.2.5 Cascade Heck Reaction/Suzuki Coupling, 232 6.2.6 Cascade Amino–/Oxopalladation/Carbopalladation Reaction, 234 6.3 Cascade Reactions Involving Alkynes, 237 6.3.1 Cascade Heck Reactions, 238 6.3.2 Cascade Heck/Suzuki Coupling, 238 6.3.3 Cationic Palladium(II)–Catalyzed Cascade Reactions, 239 6.3.4 Cascade Heck Reaction/Stille Coupling, 241 6.3.5 Cascade Heck/Sonogashira Coupling, 243 6.3.6 Cascade Sonogashira Coupling–Cyclization, 244 6.3.7 Cascade Heck and C–H Bond Functionalization, 247 6.3.8 Cascade Reactions Initiated by Oxopalladation, 253 6.3.9 Cascade Reactions Initiated by Aminopalladation, 256 6.3.10 Cascade Reactions Initiated by Halopalladation or Acetoxypalladation, 259 6.3.11 Cascade Reactions of 2–(1–Alkynyl)–alk–2–en–1–ones, 263 6.3.12 Cascade Reactions of Propargylic Derivatives, 263 6.4 Cascade Reactions Involving Allenes, 264 6.4.1 Cascade Reactions of Monoallenes, 264 6.4.2 Cross–Coupling Cyclization of Two Different Allenes, 274 6.5 Summary and Outlook, 276 Acknowledgments, 277 References, 277 7 Use of Transition Metal–Catalyzed Cascade Reactions in Natural Product Synthesis and Drug Discovery 283 Peng–Fei Xu and Hao Wei 7.1 Introduction, 283 7.2 Palladium–Catalyzed Cascade Reactions in Total Synthesis, 284 7.2.1 Cross–Coupling Reactions, 284 7.2.1.1 Heck Reaction, 284 7.2.1.2 Stille Reaction, 291 7.2.1.3 Suzuki Coupling Reaction, 297 7.2.2 Tsuji–Trost Reaction, 301 7.2.3 Other Palladium–Catalyzed Cascade Reactions in Total Synthesis, 303 7.3 Ruthenium–Catalyzed Cascade Reactions in Total Synthesis, 305 7.4 Gold–and Platinum–Catalyzed Cascade Reactions in Organic Reactions, 318 7.5 Copper–and Rhodium–Catalyzed Cascade Reactions in Organic Synthesis, 322 7.6 Summary, 326 References, 326 8 Engineering Mono–and Multifunctional Nanocatalysts for Cascade Reactions 333 Hexing Li and Fang Zhang 8.1 Introduction, 334 8.2 Heterogeneous Monofunctional Nanocatalysts, 335 8.2.1 Metal–Based Monofunctional Nanocatalysts, 335 8.2.2 Metal Oxide–Based Monofunctional Nanocatalysts, 340 8.2.3 Orgamometallic–Based Monofunctional Nanocatalysts, 340 8.2.4 Graphene Oxide–Based Monofunctional Nanocatalysts, 343 8.3 Heterogeneous Multifunctional Nanocatalysts, 344 8.3.1 Acid–Base Combined Multifunctional Nanocatalysts, 344 8.3.2 Metal–Base Combined Multifunctional Nanocatalysts, 349 8.3.3 Organometallic–Base Combined Multifunctional Nanocatalysts, 349 8.3.4 Binary Organometallic–Based Multifunctional Nanocatalysts, 350 8.3.5 Binary Metal–Based Multifunctional Nanocatalysts, 352 8.3.6 Metal–Metal Oxide Combined Multifunctional Nanocatalysts, 353 8.3.7 Organocatalyst–Acid Combined Multifunctional Nanocatalysts, 353 8.3.8 Acid–Base–Metal Combined Multifunctional Nanocatalyst, 356 8.3.9 Triple Enzyme–Based Multifunctional Nanocatalysts, 356 8.4 Conclusions and Perspectives, 359 References, 360 9 Multiple–Catalyst–Promoted Cascade Reactions 363 Peng–Fei Xu and Jun–Bing Ling 9.1 Introduction, 363 9.2 Multiple Metal Catalyst–Promoted Cascade Reactions, 364 9.2.1 Catalytic Systems Involving Palladium, 365 9.2.2 Catalytic Systems Involving Other Metals, 368 9.3 Multiple Organocatalyst–Promoted Cascade Reactions, 370 9.3.1 Catalytic Systems Combining Multiple Amine Catalysts, 371 9.3.2 Catalytic Systems Combining Amine Catalysts and Nucleophilic Carbenes, 380 9.3.3 Catalytic Systems Combining Amine and Hydrogen–Bonding Donor Catalysts, 385 9.3.4 Catalytic Systems Involving Other Organocatalysts, 390 9.4 Metal/Organic Binary Catalytic System–Promoted Cascade Reactions, 394 9.4.1 Catalytic Systems Combining Secondary Amine and Metal Catalysts, 394 9.4.2 Catalytic Systems Combining Brønsted Acid and Metal Catalysts, 404 9.4.3 Catalytic Systems Combining Hydrogen–Bonding Donor and Metal Catalysts, 411 9.4.4 Catalytic Systems Combining Other Organo–and Metal Catalysts, 413 9.5 Summary and Outlook, 415 References, 415 Index 419
- ISBN: 978-1-118-01602-2
- Editorial: Wiley–Blackwell
- Encuadernacion: Cartoné
- Páginas: 440
- Fecha Publicación: 03/12/2013
- Nº Volúmenes: 1
- Idioma: Inglés