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Acetylene Chemistry: Chemistry, Biology and Material Science

Francois Diederich (Editor), Peter J. Stang (Editor), Rik R. Tykwinski (Editor)
ISBN: 978-3-527-30781-4
528 pages
March 2005
Acetylene Chemistry: Chemistry, Biology and Material Science (3527307818) cover image

Description

Acetylenes are an important and valuable class of compounds in organic synthesis. This book expands on this historically well-established concept, while incorporating the many new developments that have widened the number of applications in this field. It remains the only handbook available that embodies all the important facets of acetylene chemistry. Following the first section on synthesis, the leading authors deal with advanced materials before turning to the properties and theory of acetylenes, while a final section looks at the biological aspects. With its range of experimental procedures, this book is a practical aid for both organic and organometallic chemists, as well as for materials scientists, biochemists, and industrial chemists.
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Table of Contents

1 Theoretical Studies on Acetylenic Scaffolds 1

1.1 Introduction 1

1.2 Linear Acetylenic Scaffolds 2

1.2.1 The Dicarbon Molecule and Acetylene 2

1.2.2 Uncapped Pure sp Carbon Chains 3

1.2.3 Capped All-sp Oligoacetylenic Chains 5

1.2.4 Hybrid sp-sp2 Oligoacetylenic Molecules 9

1.2.5 Hybrid sp-sp3 Oligoacetylenic Molecules 14

1.3 Cyclic Acetylenic Scaffolds 15

1.3.1 Hybrid sp-sp3 Rings 15

1.3.2 Hybrid sp-sp2 Rings (Dehydroannulenes) 20

1.3.3 carbo-Heteroannulenes 32

1.4 Star-Shaped Acetylenic Scaffolds 34

1.4.1 Atomic Cores 34

1.4.2 Rod Cores 34

1.4.3 Cyclic Cores 37

1.5 Cage Acetylenic Scaffolds 40

1.6 Conclusion 41

Acknowledgements 42

2 Synthesis of Heterocycles and Carbocycles by Electrophilic Cyclization of Alkynes 51

2.1 Introduction 51

2.2 Cyclization of Oxygen Compounds 51

2.2.1 Cyclization of Acetylenic Alcohols 51

2.2.2 Cyclization of Acetylenic Phenols 55

2.2.3 Cyclization of Acetylenic Ethers 57

2.2.4 Cyclization of Acetylenic Acids and Derivatives 59

2.2.5 Cyclization of Acetylenic Aldehydes and Ketones 63

2.3 Cyclization of Sulfur and Selenium Compounds 66

2.4 Cyclization of Nitrogen Compounds 67

2.4.1 Cyclization of Acetylenic Amines 67

2.4.2 Cyclization of Acetylenic Amides 70

2.4.3 Cyclization of Acetylenic Carbamates 73

2.4.4 Cyclization of Acetylenic Sulfonamides 75

2.4.5 Cyclization of Acetylenic Enamines and Imines 77

2.4.6 Cyclization of Other Acetylenic Nitrogen Functional Groups 79

2.5 Cyclization of Carbon onto Acetylenes 81

2.5.1 Cyclization of Acetylenic Carbonyl Compounds and Derivatives 81

2.5.2 Cyclization of Diacetylenes 83

2.5.3 Cyclization of Aryl Acetylenes 84

2.5.4 Cyclization of Acetylenic Organometallics 89

2.6 Conclusions 90

2.7 Representative Experimental Procedures 90

2.7.1 Synthesis of a-Methylene-g-butyrolactones by Carbonylation of 1-Alkyn-4-ols 90

2.7.2 Synthesis of 1-Alkoxyisochromenes by Cyclization of

2-(1-Alkynyl)benzaldehydes 90

2.7.3 Synthesis of 3-Aryl(vinylic)indoles by Palladium-catalyzed Cross-coupling of Aryl Halides or Vinylic Triflates and

2-(1-Alkynyl)trifluoroacetanilides 90

2.7.4 Synthesis of Pyridines by the Gold-catalyzed Cross-coupling of Ketones and Propargyl Amine 91

2.7.5 Synthesis of 4-Iodoisoquinolines by the Cyclization of Iminoalkynes 91

2.7.6 Synthesis of Cyclic Amines by Acetylene-Iminium Ion Cyclizations 91

Acknowledgements 92

3 Addition of Terminal Acetylides to CO and CN Electrophiles 101

3.1 Introduction 101

3.2 Background 103

3.3 Additions with Stoichiometric Amounts of Metal Acetylides 106

3.4 Nucleophilic CO Additions involving the Use of Zn(ii) Salts 114

3.5 Acetylene Additions to CN Electrophiles 125

3.6 Conclusion 131

3.7 Experimental Procedures 131

3.7.1 General Procedure for the Enantioselective Alkynylation of Aldehydes by the Use of Stoichiometric Amounts of Zn(OTf)2 131

3.7.2 General Procedure for the Zn(OTf)2-Catalyzed Enantioselective Alkynylation of Aldehydes 132

3.7.3 General Procedure for the Enantioselective Alkynylation of Ketones Catalyzed by Zn(salen) Complexes 132

3.7.4 General Procedure for the Zn(OTf)2-Catalyzed Diastereoselective Alkynylation of N-Glycosyl Nitrones 133

3.7.5 General Procedure for the Et2Zn-Catalyzed Diastereoselective Alkynylation of Chiral Nitrones 133

3.7.6 General Procedure for the CuBr-Catalyzed Enantioselective Preparation of Propargylamines 133

3.7.7 General Procedure for the [IrCl(COD)]2-Catalyzed Alkynylation of Imines 134

4 Transition Metal Acetylides 139

4.1 Introduction 139

4.2 General Comments 140

4.2.1 Structure and Bonding 140

4.2.2 Syntheses 141

4.2.3 Reactions 144

4.3 Titanocene- and Zirconocene-Acetylides 146

4.3.1 MCCR 146

4.3.2 M(CCR)2 148

4.3.3 M(CCR)3 148

4.3.4 Products of [Cp2M(h2-RC2R)] and [Cp*2M(h2-RC2R)] with Acetylenes 149

4.3.5 Reactions 151

4.4 Complexation of MCCM 160

4.4.1 Examples 160

4.4.2 Molecular Dynamics of Acetylides 161

4.4.3 Acetylides in the Topomerization of Alkynes 163

4.5 Summary and Outlook 165

4.6 Typical Experimental Procedures 166

4.6.1 Synthesis of a Monomeric Ti(iii) Monoacetylide [Cp*2TiCCtBu] 166

4.6.2 Synthesis of a Ti(iii) Bisacetylide Tweezer [Cp2Ti(CCtBu)2][Li(THF)] 166

4.6.3 Synthesis of a Dinuclear Ti(iii) Monoacetylide [Cp2TiC2SiMe3)]2 by CC Cleavage of a 1,3-Butadiyne 167

4.6.4 Synthesis of a Zr(iv) Bisacetylide [Cp*2Zr(CCSiMe3)2] 167

4.6.5 Synthesis of a Zirconacyclocumulene [Cp*2Zr(h4 -1,2,3,4-Me3SiC4SiMe3)] 167

Acknowledgments 168

5 Acetylenosaccharides 173

5.1 Introduction 173

5.2 Isolation of Acetylenosaccharides from Natural Sources 174

5.3 Preparation of Monoalkynylated Acetylenosaccharides 177

5.3.1 Preparation of Linear Acetylenosaccharides 177

5.3.2 Preparation of Branched-Chain Acetylenosaccharides 188

5.4 Preparation of Dialkynylated Acetylenosaccharides 193

5.4.1 Linear Dialkynylated Acetylenosaccharides 193

5.4.2 Branched Dialkynylated Acetylenosaccharides 194

5.4.2.1 4-O-Alkynyl-b-d-glucopyranosylacetylenes 195

5.5 Transformations of Acetylenosaccharides 203

5.5.1 Ring-Forming Reactions 204

5.5.2 Coupling Reactions 212

5.5.2.1 Homocoupling of Acetylenosaccharides 213

5.6 Biological and Medicinal Uses of Acetylenosaccharides 215

5.7 Experimental Protocols 215

Acknowledgements 219

6 Semiconducting Poly(arylene ethylene)s 233

6.1 Introduction 233

6.2 Synthesis 234

6.3 Conducting Properties of PArEs 236

6.4 Photophysical Properties and Interpolymer Electronic Interactions 238

6.5 Sensor Applications 247

6.6 Superstructures 249

6.7 Summary 255

6.8 General Procedures for Synthesis of PPEs 255

Acknowledgements 256

7 Polyynes via Alkylidene Carbenes and Carbenoids 259

7.1 Introduction 259

7.2 Alkylidene Carbene and Carbenoid Species 260

7.3 Alkyne Formation from Carbenes and Carbenoids 261

7.3.1 Synthesis of Acetylenes: the Fritsch–Buttenberg–Wiechell Rearrangement 261

7.3.2 Synthesis of 1,3–Butadiynes 265

7.3.3 Synthesis of 1,3,5–Hexatriynes 268

7.3.4 Tri- and Pentaynes from Free Alkylidene Carbenes 273

7.4 Toward applications 274

7.4.1 Natural Products Synthesis 274

7.4.2 Extended Arylenethynylene Derivatives 276

7.4.3 Cyclo[n]carbons 283

7.5 Linear Conjugated Polyynes 284

7.5.1 Synthesis of Triisopropylsilyl End-Capped Polyynes 285

7.5.2 Solid-State Characterization 289

7.5.3 Linear Optical Properties 291

7.5.4 Third-Order Nonlinear Optical Properties 294

7.6 Conclusions 296

7.7 Experimental Procedures 297

7.7.1 General Procedure for Friedel–Crafts Acylation 297

7.7.2 General Procedure for Dibromoolefination 297

7.7.3 General FBW Rearrangement Procedure 297

7.7.4 General Oxidative Coupling Procedure 298

Acknowledgements 298

8 Macrocycles Based on Phenylacetylene Scaffolding 303

8.1 Introduction 303

8.2 Synthetic Strategies 304

8.2.1 Intermolecular Approach 304

8.2.2 Intramolecular Approach 307

8.2.3 Comparison of the Two Pathways 311

8.3 Phenylacetylene Macrocycles 312

8.3.1 Ortho PAMs 312

8.3.2 Meta-PAMs 323

8.3.3 Para-PAMs 334

8.3.4 Mixed PAMs 335

8.4 Phenyldiacetylene Macrocycles 338

8.4.1 Ortho-PDMs 339

8.4.2 Meta-PDMs 356

8.4.3 Para-PDMs 361

8.4.4 Mixed PDMs 362

8.5 Phenyltriacetylene Macrocycles 373

8.6 Phenyltetraacetylene Macrocycles 374

8.7 Phenyloligoacetylene Macrocycles 377

8.8 Conclusions 378

8.9 Experimental 378

8.9.1 Preparation of 8 from [(t-BuO)3WCt-Bu)] Catalysis of 13 378

8.9.2 Synthesis of 8 and 10 from Copper (2-Iodophenyl)acetylide 379

8.9.3 Preparation of 31 by Pd-Catalyzed Cyclization of 29 379

8.9.4 Preparation of 122 by Pd-Mediated Cyclization of 136 379

8.9.5 Synthesis of 148 from 149 and Mo(CO)6 380

8.9.6 Preparation of 189 and 190 from 1,2-Diiodotetrafluorobenzene under Hay Conditions 380

8.9.7 Preparation of 1 by Deprotection and Cyclization of 223 380

8.9.8 Synthesis of 304 by Photolysis of Dewar Benzene 305 381

8.9.9 Preparation of 332 and 333 by Deprotection/Cyclization of 335 in situ 381

Acknowledgments 381

9 Carbon-Rich Compounds: Acetylene-Based Carbon Allotropes 387

9.1 Introduction 387

9.2 Linear Carbon Clusters 388

9.3 Carbyne 394

9.4 Linear Polyynes 397

9.5 Monocyclic Carbon Clusters: Cyclo[n]carbons 410

9.6 Three-Dimensional Multicyclic Polyynes 415

9.7 Conclusion 420

Acknowledgements 420

10 Shape-Persistent Acetylenic Macrocycles for Ordered Systems 427

10.1 Introduction 427

10.2 Ordered Systems 429

10.2.1 Host-Guest Complexes 429

10.2.2 Tubular Superstructures in Solution 433

10.2.3 Thermotropic Liquid Crystals 438

10.2.4 Two-Dimensional Organization 442

10.3 Conclusions 446

10.4 Experimental Procedures 447

10.4.1 Deprotection of a CPDMS-Protected Acetylene 447

10.4.2 Template-Based Oxidative Cyclodimerization of a Rigid Bisacetylene 447

10.4.3 Deprotection of a Macrocyclic THP-Protected Tetraphenol 448

10.4.4 Alkylation of a Macrocyclic Tetraphenol 448

10.4.5 Hydrolysis of a Macrocycle with Two Intraannular Ester Groups 448

10.4.6 Formation of a Macrocycle with Two Intraannular Thioether Groups 449

Acknowledgements 449

11 Chiral Acetylenic Macromolecules 453

11.1 Introduction 453

11.2 Chiral Acetylenic Dendrimers 454

11.3 Chiral Acetylenic Polymers 460

11.3.1 Chiral Polymers Containing Main-Chain para-Phenyleneethynylenes 460

11.3.2 Chiral Polymers Containing Main-Chain ortho-Phenyleneethynylenes 468

11.3.3 Chiral Polymers Containing Main-Chain meta-Phenyleneethynylenes 482

11.3.4 Chiral Polymers Containing Main-Chain Thienylene-Ethynylenes 483

11.3.5 Chiral Polymers Containing Side-Chain Phenyleneethynylenes 485

11.4 Summary 490

Acknowledgements 491

11.5 Experimental Procedures 491

11.5.1 Preparation of the Chiral Dendrimers – A Typical Procedure 491

11.5.2 Preparation of the Chiral Polymer (R)-18e 491

11.5.3 Preparation of the Chiral Polymer (R)-45 492

11.5.4 Preparation of the Helical Polymer (R)-85 492

Index 495

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Author Information

Francois Diederich was born in 1952 in the Grand Duchy of Luxembourg. He received his doctoral degree in 1979 from the University of Heidelberg and subsequently pursued postdoctoral studies at the University of California at Los Angeles (UCLA). After his Habilitation at the Max-Planck-Institut für medizinische Forschung, he joined in 1985 the Faculty of the Department of Chemistry and Biochemistry at UCLA where he became full professor in 1989. In 1992, he moved to the ETH Zürich as a member of the Department of Chemistry and Applied Biosciences. His research interests, documented in more than 420 publications, span from medicinal chemistry, with a focus on molecular recognition studies, to advanced fullerene and acetylene-based materials with novel optoelectronic properties.

Rik R. Tykwinski received his BS degree from the University of Minnesota-Duluth and his PhD from the University of Utah. After postdoctoral studies at the Swiss Federal Institute of Technology (ETH), Zürich (1994-97), he joined the faculty of the University of Alberta in 1997 and is now an Associate Professor of Chemistry. He has published over 75 research papers, most of which describe the synthesis and unique properties of acetylenic molecules.

Peter J. Stang is professor at the university of Utah. Beside many other prices he has received the American Chemical Society George A. Olah Award in Hydrocarbon Chemistry, 2003, the Robert W. Parry Teaching Award in Chemistry, 2000 and the American Chemical Soc. James Flack Norris Award in Physical-Organic Chemistry in 1998. Stang is the author or co-author of 370 scientific publications, including six monographs and two dozen reviews.
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Reviews

"Overall Acetylene Chemistry is a superb book that gives a broad overview of alkyne science. It is well suited and almost mandatory reading for researchers, professors, and graduate students who have an interest in alkyne chemistry. It is an excellent investment for every personal library. I will buy at least two additional copies of this really important book: one for my group and one for my bedside table, to be able to take an in-depth look at the exciting possibilities of alkyne chemistry."
Advanced Materials

"The book should be available in every library concerned with these fields. The verdict: strongly recommended."
Angewandte Chemie I.E.

"... I reviewed this important book with a great deal of personal interest. I was not disappointed..."
MRS Bulletin

"...a 'superb book.' It remains the single volume 'user-friendly' compilation that offers a broad overview of acetylene chemistry..."
E-STREAMS
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