Modern Alkyne Chemistry

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.

Autorentext
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).

Inhalt

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 CycloisomerizationNucleophile 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 AlkyneAzide Reactions 115
*Sanne Schoelen and Morten Meldal*

5.1 Introduction 115

5.2 Reviews on Cu-Catalyzed AzideAlkyne 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 Modied 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 Inuence on Cu(1) Catalysis 126

5.7.2 Catalyst StructureActivity 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 &...