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Copper Catalysis in Organic Synthesis

1. Aufl.

von: Gopinathan Anilkumar, Salim Saranya
142,99 €
Verlag:	Wiley-VCH
Format:	EPUB
Veröffentl.:	08.07.2020
ISBN/EAN:	9783527826438
Sprache:	englisch
Anzahl Seiten:	504

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Titelbeschreibung

The most current information on growing field of copper catalysis Copper Catalysis in Organic Synthesis contains an up-to-date overview of the most important reactions in the presence of copper catalysts. The contributors—noted experts on the topic—provide an introduction to the field of copper catalysis, reviewing its development, scope, and limitations, as well as providing descriptions of various homo- and cross-coupling reactions. In addition, information is presented on copper-catalyzed C–H activation, amination, carbonylation, trifluoromethylation, cyanation, and click reactions. Comprehensive in scope, the book also describes microwave-assisted and multi-component transformations as well as copper-catalyzed reactions in green solvents and continuous flow reactors. The authors highlight the application of copper catalysis in asymmetric synthesis and total synthesis of natural products and heterocycles as well as nanocatalysis. This important book: <ul> <li>Examines copper and its use in organic synthesis as a more cost-effective and sustainable for researchers in academia and industry</li> <li>Offers the first up-to-date book to explore copper as a first line catalyst for many organic reactions</li> <li>Presents the most significant developments in the area, including cross-coupling reactions, C–H activation, asymmetric synthesis, and total synthesis of natural products and heterocycles</li> <li>Contains over 20 contributions from leaders in the field</li> </ul> Written for catalytic chemists, organic chemists, natural products chemists, pharmaceutical chemists, and chemists in industry, Copper Catalysis in Organic Synthesis offers a book on the growing field of copper catalysis, covering cross-coupling reactions, C–H activation, and applications in the total synthesis of natural products.

Inhaltsverzeichnis

Preface xvii Abbreviations xix 1 Copper Catalysis: An Introduction 1 Salim Saranya and Gopinathan Anilkumar References 4 2 Cu-Catalyst in Reactions Involving Pyridinium and Indolizinium Moieties 7 Bianca Furdui, Andrea V. Dediu (Botezatu), and RodicaM. Dinica 2.1 Cu-Catalyst in Reactions Involving Pyridinium Moieties 7 2.1.1 Introduction 7 2.1.2 Synthesis and Functionalization of Pyridinium Compounds Catalyzed by Copper 7 2.1.3 Green Methods for Pyridine Synthesis 13 2.2 Cu-Catalyst in Reactions Involving Indolizinium Moieties 15 2.2.1 Introduction 15 2.2.2 Synthesis of Indolizinium Compounds Using a Copper Catalyst 15 2.2.3 Cu-Catalyzed Green Synthesis of Indolizine Moieties 19 2.3 Conclusions 21 References 21 3 Copper-Catalyzed Cross-Coupling Reactions of Organoboron Compounds 23 Jan Nekvinda and Webster L. Santos 3.1 Introduction 23 3.2 Ring Opening Cross-Coupling Reactions 24 3.3 Coupling Reactions with Atoms Other than Carbon 26 3.3.1 Amines, Amides, and Sulfonamides 27 3.3.2 Nitrones 33 3.3.3 Sulfones 35 3.3.4 Silyls 35 3.3.5 Selanyls 36 3.4 Coupling Reactions Involving Carbon 36 3.4.1 Boronic Acid Esters 36 3.4.2 Boronic Acids 41 3.4.3 Single Electron Mechanism 42 3.5 Conclusion 43 References 43 4 Cu-Catalyzed Homocoupling Reactions 51 Ganesh C. Nandi, Sundaresan Ravindra, Cholakkaparambil Irfana Jesin, Parameswaran Sasikumar, and Kokkuvayil V. Radhakrishnan 4.1 Introduction 51 4.2 Synthesis of 1,3-Diynes via Homocoupling Reactions 51 4.2.1 Synthesis of 1,3-Diynes with Homogeneous Cu Catalysis 52 4.2.1.1 Synthesis of Symmetrical 1,3-Diynes with Substrates Other than Terminal Alkynes 54 4.2.2 Synthesis of Symmetrical 1,3-Diynes with Heterogeneous Cu Catalysis 55 4.2.3 Synthesis of Macrocycles Through Intramolecular Coupling of Terminal Alkynes 56 4.3 Cu-Catalyzed Synthesis of Symmetrical Biaryls Through Homocoupling Reactions 57 4.3.1 Homocoupling of Aryl Boronic Acids 58 4.3.1.1 Homogeneous Cu-Catalyzed Homocoupling Reactions 58 4.3.1.2 Heterogeneous Copper-Catalyzed Homocoupling Reactions 58 4.3.2 Synthesis of Symmetrical Biaryls Through C–H Activation 59 4.3.3 Homocoupling of Arylstannane/Silane Derivatives 62 4.3.4 Cu-Catalyzed Homocoupling of Aryl Halides for the Synthesis of Biaryls 62 4.3.4.1 Symmetrical Biaryl Formation Using Homogeneous Copper Catalyst 62 4.3.4.2 Biaryl Formation Using Heterogeneous Cu Catalyst 65 4.3.5 Cu-Catalyzed Homocoupling of Aryl Halides for the Formation of Biaryls in Natural Products 66 4.4 Homocoupling of Alkenes 68 4.5 Summary and Conclusions 69 References 69 5 Cu-Catalyzed Organic Reactions in Aqueous Media 73 Noel Nebra and Joaquín García-Álvarez 5.1 Introduction 73 5.2 Cu-Catalyzed Azide–Alkyne Cycloaddition Reactions (CuAAC) 74 5.2.1 Ligand-Accelerated Cu(I) Catalysts 74 5.2.2 Supported Cu(I) Catalysts 75 5.2.3 Micellar Cu(I) Catalysis 77 5.2.4 Heterogeneous Catalysis: CuNPs 77 5.2.5 Miscellaneous 80 5.3 Cu-Mediated Cross-Coupling Reactions: C—C and C–Heteroatom Bond Formation 81 5.3.1 The Ullmann Coupling 81 5.3.2 The Chan–Lam–Evans (CEL) Coupling 83 5.3.3 Cu-Catalyzed Cyclization Reactions via Cross-Coupling Events 85 5.3.4 Cu-Catalyzed C—H Bond Functionalization Reactions 86 5.4 Cu-Catalyzed Hydroelementation Reactions of Double and Triple C—C Bonds 89 5.4.1 Michael-Type Additions: Enone Hydrations Enabled by Cu-Based Metallo-Hydratases 89 5.4.2 Cu-Catalyzed Hydroelementation of α,β-Unsaturated Carbonyl Compounds 90 5.4.3 Cu-Catalyzed Hydroelementation of Inactivated C—C Multiple Bonds 92 5.5 Miscellaneous 96 5.6 Summary and Conclusions 98 Acknowledgments 98 References 100 6 Cu-Catalyzed Organic Reactions in Deep Eutectic Solvents (DESs) 103 Noel Nebra and Joaquín García-Álvarez 6.1 Introduction 103 6.2 Cu-Catalyzed Azide–Alkyne Cycloaddition Reactions (CuAAC) in DESs 106 6.3 Cu-Catalyzed C—C and C—N Bond Formations in DESs 108 6.3.1 Cu-Catalyzed Sonogashira C–C Coupling Using the Eutectic Mixture 1CuCl/1Gly 108 6.3.2 Synthesis of Heterocyclic Compounds via Cu-Catalyzed Cross-Coupling Reactions 110 6.3.3 Cu-Catalyzed C—N Bond Formation in DESs 110 6.4 Cu-Catalyzed Atom Transfer Radical Polymerization Processes in DESs (SARA and ARGET) 112 6.5 Summary and Conclusions 113 Acknowledgments 114 References 114 7 Microwave-Assisted Cu-Catalyzed Organic Reactions 119 Bogdan Štefane, Helena Brodnik-?ugelj, Uroš Grošelj, Jurij Svete, and Franc Po?gan 7.1 Introduction 119 7.2 Ring-Forming Reactions 121 7.2.1 Synthesis of Heterocycles 121 7.2.1.1 Cycloadditions 121 7.2.1.2 Annulation Reactions 123 7.2.1.3 Intramolecular Cyclizations 126 7.2.1.4 Multicomponent Reactions (MCRs) 126 7.2.2 Synthesis of Carbocycles 128 7.3 Cross-Coupling Reactions 130 7.3.1 Carbon–Carbon Couplings 130 7.3.2 Carbon–Heteroatom Couplings 134 7.3.2.1 C–N Couplings 134 7.3.2.2 C–Chalcogen Couplings 138 7.4 Multicomponent Reactions 141 7.5 Miscellaneous Reactions 144 7.6 Summary and Conclusions 146 Acknowledgments 146 References 146 8 Cu-Catalyzed Asymmetric Synthesis 153 Hidetoshi Noda, Naoya Kumagai, and Masakatsu Shibasaki 8.1 Introduction 153 8.1.1 Cu-Catalyzed Asymmetric Synthesis: Scope of This Chapter 153 8.1.2 Structures of Chiral Ligands: Trends of the Last Decade 154 8.2 In Situ Generation of Cu Nucleophiles from Unsaturated Hydrocarbons 155 8.2.1 Reductive Aldol Reactions 155 8.2.2 Intramolecular Oxy- and Amidocupration 156 8.2.3 Hydrocupration of Unsaturated Compounds 158 8.2.4 Borylcupuration of Unsaturated Compounds 163 8.3 Generation of Cu Nucleophiles Under Proton Transfer Conditions 165 8.4 Summary and Conclusions 172 References 172 9 Cu-Catalyzed Click Reactions 177 Rajagopal Ramkumar and Pazhamalai Anbarasan 9.1 Introduction 177 9.2 Background 178 9.2.1 Huisgen’s Cycloaddition Reaction 178 9.2.2 Copper(I)-Catalyzed Azide–Alkyne Cycloaddition (CuAAC) 178 9.2.3 Mechanistic Study of Copper Azide–Alkyne Cycloaddition Reaction 179 9.3 CuAAC for the Synthesis of Substituted 1,2,3-Triazoles 180 9.4 Heterogeneous CuAAC Reactions 188 9.5 Ligand-Stabilized Cu(I)-Catalyzed Click Reaction 191 9.6 Synthesis of Rotaxanes and Catenanes Using CuAAC 196 9.7 Synthesis of N-Sulfonyl-1,2,3-Triazoles and Their Applications 198 9.8 CuAAC and Asymmetric Synthesis 198 9.9 CuAAC for Synthesis of Biologically Active Molecules 202 9.10 Summary 204 References 204 10 Cu-Catalyzed Multicomponent Reactions 209 Thachapully D. Suja and Rajeev S. Menon 10.1 Introduction 209 10.2 Cu-Catalyzed MCRs of Alkynes 209 10.2.1 Cu-Catalyzed Multicomponent Alkyne–Azide Cycloadditions 210 10.2.1.1 CuAAC Reactions Initiated by Azide Generation 210 10.2.1.2 CuAAC Reactions Initiated by Alkyne Generation 214 10.2.1.3 Other Multicomponent CuAAC Reactions 214 10.2.2 Cu-Catalyzed Generation and Interception of Ketenimines from Alkynes and Azides 216 10.2.3 Cu-Catalyzed Aldehyde, Alkyne, and Amine (A3) Coupling 221 10.2.3.1 A3-Coupling ReactionsThat Afford Propargyl Amine Derivatives 222 10.2.3.2 Variation of the Reaction Components in A3-Coupling 224 10.2.3.3 Asymmetric A3 (AA3)-Coupling Reactions 226 10.2.3.4 Synthetic Applications of Cu-Catalyzed A3-Coupling Reactions 227 10.3 Other Cu-Catalyzed Multicomponent Reactions 229 10.4 Summary and Conclusions 233 References 233 11 Copper-Catalyzed Aminations 239 Nissy A. Harry and Rajenahally V. Jagadeesh 11.1 Introduction 239 11.2 Copper-Catalyzed Amination of Aryl and Alkenyl Electrophiles 240 11.2.1 Ammonia as a Nucleophile 240 11.2.2 Sodium Azide as Nucleophile 241 11.2.3 Amines as Nucleophile 242 11.2.4 Mechanism of Cu-Catalyzed Amination of Aryl/Alkyl Halides 244 11.3 Chan–Lam Coupling Reaction 244 11.4 Copper-Catalyzed Hydroaminations 246 11.4.1 Hydroamination of Alkenes 247 11.4.2 Hydroamination of Alkynes 250 11.4.3 Hydroamination of Allenes 251 11.5 Copper-Catalyzed C—H amination Reactions 251 11.6 Conclusion 254 References 254 12 Cu-Catalyzed Carbonylation Reactions 261 Parameswaran Sasikumar, Thoppe S. Priyadarshini, Sanjay Varma, Ganesh C. Nandi, and Kokkuvayil V. Radhakrishnan 12.1 Introduction 261 12.2 Single Carbonylation Reactions 262 12.2.1 Copper-Catalyzed Carbonylative Coupling Reactions 262 12.2.2 Cu-Catalyzed Carboxylation Reaction 268 12.2.3 Cu-Catalyzed Oxidative Carbonylation Reactions 269 12.2.4 Carbonylative Acetylation Reaction 272 12.2.5 Aminocarbonylation Reaction 273 12.2.6 Copper-Catalyzed Oxidative Amidation 275 12.3 Cu-Catalyzed Double Carbonylation Reactions 275 12.4 Summary and Conclusions 278 References 278 13 Ligand-Free, Cu-Catalyzed Reactions 279 Muhammad F. Jamali, Sanoop P. Chandrasekharan, and Kishor Mohanan 13.1 Introduction 279 13.2 Heterocycle Synthesis 279 13.2.1 Five-Membered Heterocycles 280 13.2.2 Six-Membered Heterocycles 280 13.2.3 Benzofused Five-Membered Heterocycles Containing One Heteroatom 281 13.2.4 Benzofused Five-Membered Heterocycles Containing Two Heteroatoms 283 13.2.5 Benzofused Five-Membered Heterocycles Containing Three Heteroatoms 284 13.2.6 Benzofused Six-Membered Heterocycles 284 13.2.7 Polycyclic Compounds 286 13.2.8 Spirocyclic Compounds 286 13.3 Carbon–Heteroatom Bond Formations 289 13.3.1 C—N Bond Formation 289 13.3.2 C—O Bond Formation 291 13.3.3 C—S Bond Formation 291 13.3.4 C—P Bond Formation 295 13.3.5 C—B Bond Formation 295 13.3.6 C—Se Bond Formation 295 13.4 C–H Activation Reactions 297 13.5 Cross-coupling Reactions 299 13.6 Azide–Alkyne Cycloaddition Reactions (CuAAC) 301 13.7 Trifluoromethylation Reactions 302 13.8 Cyanation Reactions 303 13.9 Carbonylation Reactions 304 13.10 Conclusion 305 References 305 14 Copper-Catalyzed Decarboxylative Coupling 309 Firas El-Hage and Jola Pospech 14.1 Introduction 309 14.2 Copper-Catalyzed Decarboxylation of Benzoic Acids 309 14.3 Copper-Catalyzed Decarboxylation of Alkenyl Carboxylic Acids 315 14.4 Copper-Catalyzed Decarboxylation of Alkynyl Carboxylic Acids 316 14.5 Copper-Catalyzed Decarboxylation of Alkyl Carboxylic Acids 320 14.6 Summary and Conclusions 325 References 326 15 Copper-Catalyzed C–H Activation 329 Xun-Xiang Guo 15.1 Introduction 329 15.2 Carbon–Carbon Bond Formation via Cu-Catalyzed C–H Activation 329 15.2.1 Cu-Catalyzed C(sp2)–H Activation 329 15.2.2 Cu-Catalyzed C(sp3)–H Activation 332 15.3 Carbon–Heteroatom Bond Formation via Cu-Catalyzed C–H Activation 334 15.3.1 C—N Bond Formation 334 15.3.2 C—O Bond Formation 339 15.3.3 C—X Bond Formation 341 15.3.4 C—P Bond Formation 345 15.3.5 C—S Bond Formation 346 15.4 Conclusion 347 References 347 16 Aerobic Cu-Catalyzed Organic Reactions 349 Ahmad A. Almasalma and Esteban Mejía 16.1 Introduction 349 16.2 C—C Bond Formation Reactions 351 16.2.1 Cross-dehydrogenative Couplings Under Thermal Conditions 352 16.2.2 Cross-dehydrogenative Couplings Under Photochemical Conditions 354 16.3 Carbonyl Synthesis via Oxidation of Alcohols 357 16.3.1 “Copper-Only” Biomimetic Catalyst Systems 358 16.3.2 Cu/Nitroxyl “Dual” Systems 360 16.4 Summary and Conclusions 362 References 363 17 Copper-Catalyzed Trifluoromethylation Reactions 367 Dzmitry G. Kananovich 17.1 Introduction 367 17.2 Trifluoromethylation of Arenes and Heteroarenes (C(sp2)—CF3 Bond Formation) 370 17.3 Trifluoromethylation of Alkenes and Alkynes 374 17.4 Trifluoromethylation of Aliphatic Precursors (C(sp3)—CF3 Bond Formation) 378 17.4.1 Transformations via Functional Group Interconversions 378 17.4.2 Direct C(sp3)–H Trifluoromethylation 382 17.4.3 Ring-opening Trifluoromethylation 386 17.5 Copper-Mediated Formation of CF3–Heteroatom Bonds 388 17.6 Summary and Conclusions 388 References 389 18 Cu-Catalyzed Reactions for Carbon–Heteroatom Bond Formations 395 Govindasamy Sekar, Subramani Sangeetha, Anuradha Nandy, and Rajib Saha 18.1 Introduction 395 18.2 Cu-Catalyzed Reactions for Carbon–Nitrogen Bond Formations 395 18.2.1 Coupling Reactions with Ammonia and its Surrogates 396 18.2.2 Coupling Reactions with Amines 396 18.2.3 Coupling Reactions with Amides, Lactams, and Carbamates 398 18.2.4 Coupling Reactions with Protected Hydrazines and Hydroxylamines 400 18.2.5 Coupling Reactions with Guanidines 400 18.2.6 Coupling Reactions with N-Heterocycles 401 18.3 Cu-Catalyzed Reactions for Carbon–Oxygen Bond Formations 401 18.3.1 Mechanism and Presence of Cu(I) Intermediate in Ullmann Ether Synthesis 402 18.3.2 Role of Ligands in Copper-Catalyzed Ether Synthesis 403 18.3.3 Copper-Catalyzed C—O Bond Formation for Synthesizing Phenols 404 18.3.4 Copper-Catalyzed C—H Functionalization for C—O Bond Formation 405 18.3.5 Copper-Catalyzed Synthesis of Oxygen Heterocycles 405 18.3.6 Selectivity of Copper-Catalyzed C—O and C—N Bond Formation 406 18.4 Cu-Catalyzed Reactions for Carbon–Sulfur Bond Formations 407 18.5 Cu-Catalyzed Reactions for Carbon–Selenium and Carbon–Tellurium Bond Formations 413 18.6 Cu-Catalyzed Reactions for Carbon–Phosphorous Bond Formations 414 18.7 Cu-Catalyzed Reactions for Carbon–Silicon Bond Formations 415 18.8 Cu-Catalyzed Reactions for Carbon–Halogen Bond Formations 415 18.9 Conclusions 416 References 416 19 Cu-Assisted Cyanation Reactions 423 Sumanta Garai and Ganesh A. Thakur 19.1 Introduction 423 19.2 Cyanation Reaction Using CN-Containing Source 423 19.2.1 Metallic Bound CN-Source 423 19.2.1.1 Metal Cyanide 423 19.2.1.2 Potassium Ferrocyanide [K3Fe(CN)6] 427 19.2.2 Nonmetallic CN-Source 427 19.2.2.1 Acetone Cyanohydrin 427 19.2.2.2 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) 428 19.2.2.3 2,2′-Azobisisobutyronitrile (AIBN) 429 19.2.2.4 Benzyl Cyanide 429 19.2.2.5 Acetonitrile 432 19.2.2.6 Malononitrile 435 19.2.2.7 Cyanogen Iodide 436 19.2.2.8 α-Cyanoacetate 436 19.3 Cyanation Reaction Using Non-CN-Containing Source 437 19.3.1 N,N-Dimethylformamide (DMF) 437 19.3.2 Ammonium Iodide (NH4I) and N,N-Dimethylformamide (DMF) 439 19.3.3 Nitromethane 441 Acknowledgments 441 References 441 20 Application of Cu-Mediated Reactions in the Synthesis of Natural Products 443 Anas Ansari and Ramesh Ramapanicker 20.1 Introduction 443 20.2 Classification 443 20.3 Total Synthesis Employing Cu-Catalyzed C–C Coupling Reactions 445 20.3.1 (+)-Nocardioazine B 445 20.3.2 (−)-Rhazinilam 447 20.3.3 Isohericenone and Erinacerin A 447 20.3.4 (+)-Piperarborenine B 449 20.3.5 Macrocarpines D and E 450 20.4 Total Synthesis Employing Cu-Catalyzed C–N Coupling Reactions 454 20.4.1 (−)-Aspergilazine A 454 20.4.2 (−)-Psychotriasine 454 20.4.3 (−)-Indolactam V 455 20.4.4 (−)-Palmyrolide A 458 20.5 Total Synthesis Employing Cu-Catalyzed C–O Coupling Reactions 458 20.5.1 (±})-Untenone A 458 20.5.2 Coumestrol and Aureol 460 20.6 Total Synthesis Employing Cu-Catalyzed Domino Reactions 463 20.6.1 (±})-Sacidumlignan D 463 20.7 Conclusion 463 References 465 Index 469

Autorenportrait

Gopinathan Anilkumar, PhD., is professor of organic chemistry at the School of Chemical Sciences, Mahatma Gandhi University in Kottayam, Kerala, India. His research interests are in the areas of organic synthesis, medicinal chemistry, heterocyclic chemistry and catalysis, particularly on ruthenium-, iron-, zinc-, copper-, manganese-, cobalt- and nickel-catalyzed reactions. Salim Saranya is a PhD student in the group of Prof. Gopinathan Anilkumar at the School of Chemical Sciences, Mahatma Gandhi University, Kottayam, Kerala, India.