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Modern Alkyne Chemistry Catalytic and Atom-Economic Transformations

by: Trost, Barry M.; Li, Chao-Jun

Modern Alkyne Chemistry Catalytic and Atom-Economic Transformations

by: Trost, Barry M.; Li, Chao-Jun

ISBN 13:
9783527335053
ISBN 10:
3527335056
Edition: 1st
Format: Hardcover
Copyright: 02/09/2015
Publisher: Wiley-VCH

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Modern Alkyne Chemistry Catalytic and Atom-Economic Transformations > ISBN13: 9783527335053

Summary

A comprehensive and up-to-date overview of alkyne chemistry, taking into account the progress made over the last two decades. The experienced editors are renowned world leaders in the field, while the list of contributors reads like a "Who's Who" of synthetic organic chemistry.
The result is a valuable reference not only for organic chemists at universities and in the chemical industry, but also for biologists and material scientists involved in the modern synthesis of organic compounds and materials.

Author Biography

Professor Barry M. Trost obtained a Ph.D. at the Massachusetts Institute of Technology (Cambridge, USA) and directly moved to the University of Wisconsin (USA) where he was promoted to Professor of Chemistry in 1969 and subsequently became the Vilas Research Professor in 1982. He joined the faculty at Stanford (USA) as Professor of Chemistry in 1987 and became Tamaki Professor of Humanities and Sciences in 1990. Professor Trost has received a number of awards, including the ACS Award in Pure Chemistry (1977), the ACS Award for Creative Work in Synthetic Organic Chemistry (1981), the Alexander von Humboldt Stiftung Award (1984), Arthur C. Cope Scholar Award (1989), the Belgian Organic Synthesis Symposium Elsevier Award (2000), the Nichols Medal (2000), the Yamada Prize (2001), the ACS Cope Award (2004), and the Nagoya Medal (2008). Professor Trost has been elected a Fellow of the American Academy of Sciences (1982) and a member of the National Academy of Sciences (1980). He has served as editor and on the editorial board of many books and journals, including being Associate Editor of the "Journal of the American Chemical Society" (1974-80). He has held over 125 special university lectureships and presented over 270 plenary lectures at national and international meetings. He has published two books and over 900 scientific articles. He edited the compendium "Comprehensive Organic Synthesis" consisting of nine volumes and serves on the editorial board for the reference databases "Science of Synthesis" (Thieme) and "Reaxys" (Elsevier).

Professor Chao-Jun Li received his Ph.D at McGill University (Montreal, Canada) and did a NSERC Postdoctoral Fellow at Stanford University (USA). He was on the faculty at Tulane University (New Orleans, USA) until 2003. Since 2003, he has been at McGill University where he currently holds a Canada Research Chair (in Green Chemistry) and an E. B. Eddy Chair Professorship. He has published over 300 scientific publications and received numerous awards including the US Presidential Green Chemistry Challenge Award and the Canadian Green Chemistry and Engineering Award. He is a Fellow of the Royal Society of Canada (Academy of Science) and is an Associate Editor for "Green Chemistry" of the Royal Society of Chemistry (UK).

List of Contributors XIII

Preface XVII

1 Introduction 1
Chao-Jun Li and Barry M. Trost

1.1 History of Alkynes 1

1.2 Structure and Properties of Alkynes 2

1.3 Classical Reactions of Alkynes 2

1.4 Modern Reactions 4

1.5 Conclusion 6

References 7

Part I Catalytic Isomerization of Alkynes 9

2 Redox Isomerization of Propargyl Alcohols to Enones 11
Barry M. Trost

2.1 Introduction 11

2.2 Base Catalysis 12

2.3 Ru Catalyzed 15

2.4 Rh Catalysis 20

2.5 Palladium Catalysis 22

2.6 Miscellaneous 24

2.7 Conclusions 25

References 25

3 Carbophilic Cycloisomerization Reactions of Enynes and Domino Processes 27
Jean-Pierre Genet, Patrick Y. Toullec, and Véronique Michelet

3.1 Introduction and Reactivity Principles 27

3.1.1 The Reactivity of Carbophilic Lewis Acids in the Presence of Enyne Substrates 27

3.2 Skeletal Rearrangement Reactions in the Absence of Nucleophiles 28

3.2.1 Synthesis of Dienes (1,3- and 1,4-Dienes) 28

3.2.2 Cycloisomerization Reactions Involving Activated Alkene Partners: Conia-Ene Reaction and Related Transformations 32

3.2.3 Formation of Bicyclic Derivatives 37

3.2.3.1 Formation of Bicyclopropanes 37

3.2.3.2 Formation of Bicyclobutenes 41

3.2.3.3 Formation of Larger Rings via Cycloisomerization- Rearrangements 42

3.3 Enyne Domino Processes 44

3.3.1 Domino Enyne Cycloisomerization–Nucleophile Addition Reactions 44

3.3.1.1 Oxygen and Nitrogen Nucleophiles 45

3.3.1.2 Carbon Nucleophiles 54

3.4 Conclusion 61

References 62

4 Alkyne Metathesis in Organic Synthesis 69
Alois Fürstner

4.1 Introduction 69

4.2 Mechanistic Background and Classical Catalyst Systems 70

4.3 State-of-the-Art Catalysts 75

4.4 Basic Reaction Formats and Substrate Scope 80

4.5 Selected Applications 85

4.5.1 Dehydrohomoancepsenolide 85

4.5.2 Olfactory Macrolides 86

4.5.3 Haliclonacyclamine C 87

4.5.4 Hybridalactone 88

4.5.5 Cruentaren A 88

4.5.6 The Tubulin-Inhibitor WF-1360F 89

4.5.7 Neurymenolide A 91

4.5.8 Leiodermatolide 91

4.5.9 Tulearin C 94

4.5.10 The Antibiotic A26771B 95

4.5.11 Lactimidomycin 96

4.5.12 Citreofuran 97

4.5.13 Polycavernoside 98

4.5.14 Amphidinolide F 99

4.5.15 Spirastrellolide F Methyl Ester 101

4.6 Conclusions 102

References 108

Part II Catalytic Cycloaddition Reactions 113

5 Alkyne–Azide Reactions 115
Sanne Schoﬀelen and Morten Meldal

5.1 Introduction 115

5.2 Reviews on Cu-Catalyzed Azide–Alkyne Cycloaddition 117

5.3 Mechanistic Considerations on the Cu(1) Catalysis 118

5.4 The Substrates for CuAAC 121

5.5 The Environment 124

5.6 Modiﬁed 1,2,3-Triazoles and CuAAC Side Reactions 125

5.6.1 Oxidative Couplings of Cu(1)–Triazole Complexes 125

5.6.2 Reactions in the 5-Position of Triazoles 125

5.6.3 Side Reactions due to Substrate Instability 126

5.7 The Catalyst 126

5.7.1 Recent Ligands and their Inﬂuence on Cu(1) Catalysis 126

5.7.2 Catalyst Structure–Activity Relationship 128

5.7.3 In Situ Generated CuAAC: Electro-, Photo-, and Self-Induced “Click” 130

5.8 Optimizing Conditions for CuAAC Reactions 131

5.9 CuAAC in Biological Applications 132

5.10 Biocompatibility of the CuAAC Reaction 133

References 137

6 Catalytic Cycloaddition Reactions 143
Fiona R. Truscott, Giovanni Maestri, Raphael Rodriguez, and Max Malacria

6.1 Introduction 143

6.2 (2 + 2) Cycloaddition 143

6.3 (3 + 2) and (2 + 1) Cycloaddition 145

6.4 (4 + 2) Cycloaddition 146

6.5 (5 + 1) and (4 + 1) Cycloadditions 149

6.6 (5 + 2) Cycloaddition 150

6.7 (6 + 2) Cycloaddition 152

6.8 (2 + 2 + 1) Cycloaddition 153

6.9 (2 + 2 + 2) Cycloaddition 155

6.10 (3 + 2 + 1) Cycloaddition 158

6.11 (3 + 2 + 2) Cycloaddition 159

6.12 (4 + 2 + 1) and (4 + 2 + 2) Cycloaddition 160

6.13 (4 + 3 + 2) Cycloaddition 163

6.14 (5 + 2 + 1) and (5 + 1 + 2 + 1) Cycloadditions 163

6.15 (2 + 2 + 1 + 1) and (2 + 2 + 2 + 1) Cycloadditions 164

6.16 (2 + 2 + 2 + 2) Cycloaddition 165

6.17 Conclusions 166

References 166

Part III Catalytic Nucleophilic Additions and Substitutions 171

7 Catalytic Conjugate Additions of Alkynes 173
Naoya Kumagai and Masakatsu Shibasaki

7.1 Introduction 173

7.2 Metal Alkynylides as Nucleophiles 173

7.2.1 Conjugate Addition of Metal Alkynylides 173

7.2.1.1 Conjugate Addition of Metal Alkynylides to s-cis α,β-Enones 173

7.2.1.2 Conjugate Addition of Metal Alkynylides with a Catalytic Promoter 176

7.2.1.3 Conjugate Addition of Metal Alkynylides with Stoichiometric Promoters 177

7.2.2 Enantioselective Conjugate Addition of Metal Alkynylides 178

7.2.2.1 Use of a Stoichiometric Amount of Chiral Sources 178

7.2.2.2 Catalytic Enantioselective Conjugate Addition of Metal Alkynylides 180

7.3 Direct Use of Terminal Alkynes as Pronucleophiles 182

7.3.1 Direct Catalytic Conjugate Addition of Terminal Alkynes 182

7.3.1.1 Introduction 182

7.3.1.2 Addition to Vinyl Ketones and Acrylates 182

7.3.1.3 Addition to β-Substituted α,β-Enones 184

7.3.2 Enantioselective Direct Catalytic Conjugate Addition of Terminal Alkynes 188

7.4 Summary and Conclusions 196

References 196

8 Catalytic Enantioselective Addition of Terminal Alkynes to Carbonyls 201
Barry M. Trost and Mark J. Bartlett

8.1 Introduction 201

8.2 Metallation of Terminal Alkynes: Formation of Alkynyl Nucleophiles 203

8.2.1 Deprotonation of Terminal Alkynes 203

8.2.2 Oxidative Insertion and Ligand Exchange: Formal Metallation of Terminal Alkynes 205

8.3 Ligand-Catalyzed Alkyne Additions with Stoichiometric Quantities of Metal 207

8.3.1 Addition of Alkynylzinc Nucleophiles to Aldehydes, Ketones, and Imines 207

8.3.2 Titanium-Catalyzed Alkynylation of Aldehydes and Ketones 217

8.3.3 Asymmetric Boron-Catalyzed Alkyne Additions to Aldehydes 222

8.4 Alkyne Additions with Catalytic Amounts of Metal 222

8.4.1 Asymmetric Alkyne Additions to Aldehydes and Ketones Catalyzed by Zinc Salts 222

8.4.2 Indium-Catalyzed Alkyne Additions to Aldehydes 224

8.4.3 Chromium-Catalyzed Alkynylation of Aldehydes with Haloacetylenes 225

8.4.4 Copper-Catalyzed Alkynylation of Aldehydes and Triﬂuoromethyl Ketones 227

8.4.5 Palladium-Catalyzed Additions to α,β-Unsaturated Carbonyls and Triﬂuoropyruvate 229

8.4.6 Enantioselective Ruthenium-Catalyzed Alkynylation of Aldehydes 230

8.4.7 Rhodium-Catalyzed Alkynylation of α-Ketoesters 231

8.5 Concluding Remarks 232

References 233

9 Catalytic Nucleophilic Addition of Alkynes to Imines: The A³ (Aldehyde–Alkyne–Amine) Coupling 239
Nick Uhlig, Woo-Jin Yoo, Liang Zhao, and Chao-Jun Li

9.1 A³ Couplings Involving Primary Amines 239

9.2 A³ Couplings Involving Secondary Amines 242

9.3 Alkyne Additions with Reusable Catalysts 244

9.4 Asymmetric Alkyne Addition Reactions 246

9.4.1 Asymmetric A³-Type Couplings with Primary Amines 246

9.4.2 Asymmetric A³-Type Couplings with Secondary Amines 250

9.5 Alkyne Additions to Imines in Tandem Reactions 251

9.5.1 A³ Coupling with Tandem Cycloisomerizations Involving the Alkyne Triple Bond 252

9.5.2 Tandem Processes Involving Other Transformations of the Alkyne Triple Bond 257

9.5.3 Tandem Processes Involving Decarboxylations 259

9.5.4 Tandem Processes Involving Both the Amine and the Alkyne 260

9.6 Conclusion 262

References 263

10 The Sonogashira Reaction 269
Rafael Chinchilla and Carmen Ná jera

10.1 Introduction 269

10.2 Palladium–Phosphorous Catalysts 270

10.2.1 Unsupported Palladium–Phosphorous Catalysts 270

10.2.1.1 Copper-Cocatalyzed Reactions 270

10.2.1.2 Copper-Free Reactions 273

10.2.2 Supported Palladium–Phosphorous Catalysts 274

10.2.2.1 Copper-Cocatalyzed Reactions 274

10.2.2.2 Copper-Free Reactions 275

10.3 Palladium–Nitrogen Catalysts 276

10.3.1 Unsupported Palladium–Nitrogen Catalysts 276

10.3.2 Supported Palladium–Nitrogen Catalysts 277

10.4 N-Heterocyclic Carbene (NHC)-Palladium Catalysts 278

10.4.1 Unsupported NHC-Palladium Catalysts 278

10.4.2 Supported NHC-Palladium Catalysts 279

10.5 Palladacycles as Catalysts 280

10.5.1 Unsupported Palladacycles as Catalysts 280

10.5.2 Supported Palladacycles as Catalysts 281

10.6 Ligand-Free Palladium Salts as Catalysts 282

10.6.1 Unsupported Ligand-Free Palladium Salts as Catalysts 282

10.6.2 Supported Ligand-Free Palladium Salts as Catalysts 283

10.7 Palladium Nanoparticles as Catalysts 283

10.7.1 Unimmobilized Palladium Nanoparticles as Catalysts 283

10.7.2 Immobilized Palladium Nanoparticles as Catalysts 284

10.7.2.1 Copper-Cocatalyzed Reactions 285

10.7.2.2 Copper-Free Reactions 285

10.8 Non-Palladium-Based Catalysts 287

10.9 Mechanistic Considerations 289

10.10 Summary and Conclusions 291

References 291

Part IV Other Reactions 299

11 Catalytic Dimerization of Alkynes 301
Sergio E. Garc´ıa-Garrido

11.1 Introduction 301

11.2 Dimerization of Alkynes Catalyzed by Iron, Ruthenium, and Osmium Complexes 302

11.2.1 Homo-Coupling of Terminal Alkynes 302

11.2.2 Cross-Dimerization of Alkynes 310

11.3 Dimerization of Alkynes Catalyzed by Cobalt, Rhodium, and Iridium Complexes 311

11.3.1 Homo-Coupling of Terminal Alkynes 311

11.3.2 Cross-Dimerization of Alkynes 315

11.4 Dimerization of Alkynes Catalyzed by Nickel, Palladium, and Platinum Complexes 317

11.4.1 Homo-Coupling of Terminal Alkynes 317

11.4.2 Cross-Dimerization of Alkynes 320

11.5 Dimerization of Alkynes Catalyzed by Group 3, Lanthanide, and Actinide Complexes 322

11.6 Dimerization of Alkynes Catalyzed by Titanium, Zirconium, and Hafnium Complexes 325

11.7 Dimerization of Alkynes Catalyzed by Other Compounds 326

11.8 Summary and Conclusions 327

Acknowledgments 327

References 328

12 The Oxidative Dimerization of Acetylenes and Related Reactions: Synthesis and Applications of Conjugated 1,3-Diynes 335
Jean-Philip Lumb

12.1 Introduction 335

12.2 Syntheses of Conjugated 1,3-Diynes 336

12.3 Scope and Limitation of the Alkyne Dimerization Reaction 338

12.3.1 Choice of Copper Salt 338

12.3.2 Choice of Solvent 339

12.3.3 Substituents on the Alkyne and Basic Additives 339

12.3.4 Additional Metals 340

12.4 Scope and Limitation of Copper-Catalyzed Hetero-Coupling Reactions 340

12.5 The Cadiot–Chodkiewicz Reaction 341

12.6 Palladium-Catalyzed Acetylenic Coupling Reactions 343

12.7 Alternative Methods for the Synthesis of Diynes 344

12.8 Mechanism of Alkyne Homo-Coupling Reactions 344

12.9 Mechanism of Alkyne Hetero-Coupling Reactions 347

12.10 Utility of 1,3-Diynes in the Synthesis of Natural Products 349

12.11 Synthetic Utility of Conjugated 1,3-Diynes 351

12.12 Utility of 1,3-Diynes in Materials Science 355

12.13 Conclusion 359

References 359

13 The Alkyne Zipper Reaction in Asymmetric Synthesis 365
Kenneth Avocetien, Yu Li, and George A. O’Doherty

13.1 Introduction 365

13.2 Mechanism of KNH2/NH3 Isomerization 366

13.3 Mechanism of KAPA Isomerization 368

13.4 Applications in Natural Products 370

13.4.1 Galacto-Sugar γ-Lactones 371

13.4.2 Galacto-Sugar δ-Lactones 371

13.4.3 (-)–Apicularen A 371

13.4.4 Milbemycin β3 373

13.4.5 Cryptocaryols A and B 373

13.4.6 Tricolozin A 374

13.4.7 Elenic Acid 376

13.4.8 Daumone 377

13.4.9 (+)–Broussonetine G 379

13.4.10 Cladospolides A, B, C, iso-Cladospolide B and (ent) Cladospolide D 379

13.4.11 Shingolipid Analogs 384

13.4.12 Irciniasulfonic Acids 386

13.4.13 Clathculins A and B 386

13.4.14 Cephalosporolide H 387

13.4.15 (+)–Aspicilin 389

13.4.16 Merremoside D 389

13.4.17 Aspergillide B 392

13.5 Conclusion 393

References 393

Index 395

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