Raquel P. Herrera, Eugenia Marqués-López

Multicomponent Reactions

Concepts and Applications for Design and Synthesis

• Gebundenes Buch

Produktbeschreibung

Addressing a dynamic aspect of organic chemistry, this book describes synthetic strategies and applications for multicomponent reactions - including key routes for synthesizing complex molecules.

- Illustrates the crucial role and the important utility of multicomponent reactions (MCRs) to organic syntheses
- Compiles novel and efficient synthetic multicomponent procedures to give readers a complete picture of this class of organic reactions
- Helps readers to design efficient and practical transformations using multicomponent reaction strategies
- Describes reaction background, applications to synthesize complex molecules and drugs, and reaction mechanisms

Produktdetails

• Verlag: Wiley & Sons
• 1. Auflage
• Seitenzahl: 528
• Erscheinungstermin: 27. April 2015
• Englisch
• Abmessung: 286mm x 221mm x 33mm
• Gewicht: 1565g
• ISBN-13: 9781118016008
• ISBN-10: 1118016009
• Artikelnr.: 42200660

Autorenporträt

Raquel P. Herrera, PhD, is Tenured Scientist of the Spanish National Research Council (CSIC) at the ISQCH-University of Zaragoza. Her research interests are focused on asymmetric organocatalysis and its applications. Eugenia Marqués-López, PhD, is an assistant professor at the University of Zaragoza. She performs her research on new catalytic methods, mainly based on asymmetric organocatalysis at the Institute of Chemical Synthesis and Homogeneous Catalysis (ISQCH-CSIC).

Inhaltsangabe

List of Contributors xii Preface xiii List of Abbreviations xv 1
Introduction: Multicomponent Strategies 1 General Introduction 1 1.1 Basic
Concepts 3 1.1.1 Clarifying Terminology: One?]Pot, Domino/Cascade, Tandem,
and MCRs 3 1.1.2 Using Rational Design to Discover New MCRs 3 1.1.3
Discovering New MCRs with Automated Combinatorial Reaction Finding 5 1.1.4
Computational and Analytical Tools to Study MCRs 7 1.1.5
Diversity?]Oriented Synthesis and Biology?]Oriented Synthesis 7 1.1.6
Optimization of MCRs 7 1.2 Catalysis in MCRs and Various Synthetic
Approaches 8 1.2.1 Organocatalysis in MCRs 8 1.2.2 Organometallic Catalysis
in MCRs 8 1.2.3 Biocatalysis in MCRs 8 1.2.4 Combining Different Types of
Catalysis 8 1.2.5 Other Methods 9 1.3 Green Chemistry 10 1.3.1 Atom Economy
10 1.3.2 Using Green Solvents 11 1.3.3 Solventless MCRs 11 1.3.4
Heterogeneous Catalysis in MCRs 11 1.4 Importance and Evolution 12
References 12 2 Organocatalytic Asymmetric Multicomponent Reactions 16 2.1
Introduction 16 2.2 Three?]Component Mannich Reaction 17 2.3 Cycloaddition
Reaction 26 2.4 Organocatalytic Multicomponent Domino Asymmetric Reactions
29 2.4.1 Michael?]Type Multicomponent Process: Cyclic Carbon Frameworks 30
2.4.2 Miscellaneous Domino Reactions 49 2.5 Development of Drug
Intermediates 58 2.6 Miscellaneous Reaction 65 2.7 Conclusions 66
References 66 3 Metal?]Catalyzed Multicomponent Reactions 72 3.1
Introduction 72 3.2 Palladium?]Catalyzed Mcrs 72 3.2.1 Palladium?]Catalyzed
Carbonylation Reactions 72 3.2.2 Palladium?]Catalyzed Mcrs Involving
Isocyanides 74 3.2.3 Carbopalladation of Unsaturated C"?C pi?]Components 76
3.2.4 Amines as Building Blocks 80 3.3 Nickel?]Catalyzed Mcrs 83 3.3.1
Nickel?]Catalyzed Cross?]Trimerization of Alkynes 83 3.3.2
Nickel?]Catalyzed pi?]Systems Couplings 86 3.3.3 Ni?]Catalyzed Reductive
Conjugate Addition 88 3.4 Group 11 Metal?]Catalyzed Mcrs 91 3.4.1
Copper?]Catalyzed Azide-Alkyne Cycloaddition 91 3.4.2 A3?]Coupling 94 3.4.3
Miscellaneous 101 3.5 Rhodium?]Catalyzed Mcrs 101 3.5.1 Rhodium?]Catalyzed
Mcrs via Onium Ylide Intermediates 101 3.5.2 Rhodium?]Catalyzed
Three?]Component Cross?]Addition Reactions 108 3.6 Group 8 Metal?]Catalyzed
Mcrs 111 3.6.1 Iron?]Catalyzed Mcrs 111 3.6.2 Ruthenium?]Catalyzed Mcrs 113
3.7 Conclusions 117 References 117 4 Multicomponent Reactions with
Organoboron Compounds 127 4.1 Introduction 127 4.2 Catalytic Mcrs with
Organoboron Compounds 127 4.2.1 Cobalt?]Catalyzed Mcrs Containing
Organoboron Compounds 127 4.2.2 Palladium?]Catalyzed Mcrs Containing
Organoboron Compounds 128 4.3 Multicomponent Assembly of Organoboron
Compounds: Efficient Approach to Supramolecular Chemistry 128 4.4
Multicomponent Petasis?]Borono-Mannich Reaction 132 4.4.1 Organocatalytic
Enantioselective Petasis?]Type Reaction 133 4.4.2 Metal?]Catalyzed
Four?]Component PBM Reaction 134 4.4.3 Synthetic Applications of PBM 135
4.5 Allenylborates in Mcrs 140 4.6 Multicomponent
Hetero?]Diels-Alder/Allylboration 141 4.6.1 Chiral Catalyzed One?]Pot [4 +
2] Cycloaddition/Allylboration 141 4.6.2 Polymer?]Supported Mcrs 141 4.7
Palladium?]Catalyzed Asymmetric Allene Diboration/alpha?]Aminoallylation
143 4.8 Synthetic Applications of Boron?]Based Mcrs 143 4.9 Conclusion 146
References 146 5 Carbene?]Promoted Multicomponent Reactions 149 5.1
Introduction 149 5.2 Mcrs Involving Carbenes as Key Components 149 5.2.1
Mcrs of Dimethoxycarbenes 149 5.2.2 Mcrs of NHCs 150 5.2.3 FCCs as
Reagents: Approach to Highly Substituted Carbo?] and Heterocycles 158 5.3
Mcrs Involving Carbenes as Catalysts 162 5.3.1 Nhcs as Organocatalysts in
Mcrs 162 5.3.2 Metal?]Catalyzed Mcrs Involving Nhcs as Ligands 174 5.4
Synthetic Utility 190 5.4.1 Carbenes as Components 190 5.4.2 Nhcs as
Catalysts/Ligand 190 5.5 Conclusion 193 References 193 6 Multicomponent
Reactions in the Synthesis of Target Molecules 198 6.1 Introduction 198 6.2
Mcrs in Drug Discovery and for the Synthesis of Biologically Important
Molecules 198 6.3 Synthesis of Natural Products in an Efficient Manner 200
6.4 Heterocycles as Key Substrates in Mcrs 205 6.4.1 Synthesis of Indoles
206 6.4.2 Synthesis of Fused Polyheterocycles 211 6.4.3 Synthesis of
Spiro?]Type Polyheterocyclic Compounds 217 6.4.4 Synthesis of DHPMs and
Thiazines 224 6.4.5 Synthesis of Pyrroles 229 6.5 Amino Acid Derivatives by
Mcrs 233 6.6 Industrial Applications 236 6.7 Conclusion 239 References 239
7 Recent Advances in the Ugi Multicomponent Reactions 247 7.1 Introduction
247 7.2 Ugi Three?]Component Reactions 247 7.3 Ugi Four?]Component
Reactions 254 7.4 Five?], Six?], Seven?], and Eight?]Component Reactions
Based on the Ugi Reaction 258 7.5 Ugi Postmodification Processes 265 7.6
Ugi-Smiles Approach 270 7.7 Ugi-Smiles Postmodification Processes 274 7.8
Conclusion 278 References 278 8 Passerini Multicomponent Reactions 283 8.1
Introduction 283 8.2 O?]Alkylative and Silylative Passerini
Three?]Component Reactions 283 8.2.1 O?]Arylative Passerini
Three?]Component Reactions 283 8.2.2 Metal?]Catalyzed O?]Alkylative
Passerini Three?]Component Reactions 284 8.2.3 O?]Silylative Passerini
Three?]Component Reactions 285 8.3 Passerini 3CR Under Oxidative Conditions
286 8.3.1 Metal?]Catalyzed Oxidation Passerini 3CR 286 8.4 Synthesis of
Macrocycles by a Passerini Reaction 287 8.5 Enantioselective
Metal?]Catalyzed Passerini Reaction 290 8.6 Synthesis of Pharmacologically
Important Peptidomimetics 292 8.7 Multicomponent Passerini Approach to
Important Targets 293 8.8 alpha?]Hydroxycarboxamide, an Important
Intermediate for Chemical Synthesis 297 8.9 Passerini 3CR under
Eco?]Friendly Reaction Conditions 299 8.9.1 Aqueous Media 299 8.9.2 Ionic
Liquids and Peg 299 8.9.3 Solvent?]Free Conditions 300 8.9.4 MW?]Assisted
Passerini Reaction 300 8.10 Conclusions 301 References 302 9 Biginelli
Multicomponent Reactions 306 9.1 Introduction 306 9.2 Mechanism 306 9.3
Chiral Lewis?] and Brønsted Acid?]Catalyzed Biginelli Reactions 308 9.4
Brønsted Base?]Catalyzed One?]Pot Three?]Component Biginelli?]Type
Reactions 310 9.5 Organocatalytic Enantioselective Biginelli Reactions 311
9.5.1 Chiral Brønsted Acid?]Organocatalyzed Biginelli Reactions 311 9.5.2
Aminocatalyzed Biginelli Reactions 313 9.6 Variations of the Traditional
Biginelli Condensation 318 9.7 Heterocycles beyond the DHPMs 318 9.8
Important Targets 319 9.9 Conclusion 325 References 325 10 Bucherer-Bergs
And Strecker Multicomponent Reactions 331 10.1 Bucherer-Bergs Reaction 331
10.1.1 Introduction 331 10.1.2 Comparative Stereochemical Course 331 10.1.3
Synthesis of Five?]Membered Heterocycles 331 10.1.4 Metal?]Catalyzed
Synthesis of Hydantoin Derivatives 334 10.1.5 Modified Bucherer-Bergs
Reaction 336 10.1.6 Synthesis of alpha?]Amino Acids via Hydantoin
Intermediate 338 10.1.7 Synthesis of Diaminodicarboxylic Acids 339 10.2 Mc
Strecker Reaction 340 10.2.1 Introduction 340 10.2.2 MC Strecker Reaction
Using Aldehyde 341 10.2.3 Strecker?]Type Reaction Using Ketones 344 10.2.4
Catalyst?]Free Strecker Reactions in Water 344 10.2.5 Catalyst?]Free
Strecker Reactions under Solvent?]Free Conditions 347 10.2.6
Metal?]Catalyzed Strecker?]Type Reaction 348 10.2.7 Organocatalytic Mc
Strecker Reaction 348 10.2.8 Efficient Heterogeneous Catalysis for the
Synthesis of alpha?]Aminonitriles 351 10.2.9 Synthetic Utility 351 10.3
Conclusions 352 References 352 11 Unusual Approach for Multicomponent
Reactions 358 11.1 Zeolite?]Catalyzed Mcrs 358 11.1.1 Heterogeneous Hybrid
Catalyst 358 11.2 Mw?]Assisted Three?]Component Reactions 359 11.2.1
Synthesis of Natural Products 361 11.3 Ionic Liquid?]Promoted Mcrs 363 11.4
Mcrs under Solvent?]Free Conditions 364 11.5 Mcrs in Aqueous Media 370 11.6
High?]Pressure Promoted Mcrs 373 11.7 Three?]Component Reactions Using
Supported Reagents 375 11.8 Conclusion 376 References 377 12 E ssential
Multicomponent Reactions I 382 12.1 Radziszewski Reactions (Imidazole
Synthesis) 382 12.1.1 Introduction 382 12.1.2 Modified Radziszewski
Reactions: Efficient Tool for the Synthesis of Substituted Imidazoles 382
12.2 Sakurai Mcrs 388 12.2.1 Introduction 388 12.2.2 Synthesis of
Homoallylic Ethers 388 12.2.3 Synthesis of Homoallylic Amines: Aza?]Sakurai
391 12.3 Gewald Mcrs 394 12.3.1 Introduction 394 12.3.2 Easy Protocol for
Synthesizing 2?]Aminothiophene Derivatives 395 12.4 Kabachnik-Fields
Reactions 396 12.4.1 Introduction 396 12.4.2 Straightforward Synthesis of
alpha?]Amino Phosphonates 398 12.5 Conclusion 401 References 403 13 E
ssential Multicomponent Reactions Ii 416 13.1 Knoevenagel Reactions in
Multicomponent Syntheses 416 13.1.1 Introduction 416 13.1.2 Domino
Knoevenagel/Hetero?]Diels-Alder Reaction and Pyran Syntheses 419 13.1.3
Useful Syntheses of Heterocycles: 1,4?]Dihydropyridine and Diazine
Syntheses 427 13.1.4 Useful Syntheses of Heterocycles: Various Heterocyclic
Scaffolds 437 13.1.5 Other Knoevenagel Combinations 442 13.2
Yonemitsu?]Type Trimolecular Condensations 448 13.2.1 Introduction and
Mechanistic Aspects 448 13.2.2 Applications of the Original Yonemitsu
Trimolecular Condensation 449 13.2.3 Yonemitsu?]Type Reactions and
Tetramolecular Condensations 451 13.3 Mcrs Involving Meldrum's Acid 457
13.3.1 Introduction 457 13.3.2 Applications and DOS 458 13.3.3 Meldrum's
Acid as Synthetic Equivalent 461 13.3.4 Meldrum's Acid as Malonic Acid
Equivalent 464 13.4 Povarov Mcrs 466 13.4.1 Introduction 466 13.4.2
Mechanistic Aspects 466 13.4.3 Efficient Synthesis of
1,2,3,4?]Tetrahydroquinolines 468 13.4.4 Efficient Synthesis of Quinolines
470 13.5 Hantzsch Multicomponent Synthesis of Heterocycles 472 13.5.1
Introduction 472 13.5.2 Catalysis and Mechanism 474 13.5.3 Syntheses of
1,4?]Dihydropyridines and Their Oxidation to Pyridines 475 13.5.4
Multicomponent Pyrrole Syntheses 480 13.6 Conclusions 482 References 482
INDEX 496