Preparative Acetylenic Chemistry (eBook)

Front Cover 1
Preparative Acetylenic Chemistry 4
Copyright Page 5
Preface 8
Table of Contents 10
Chapter I. General Practical Information 14
1. Introduction 14
2. Laboratory Equipment and Techniques for the Procedures in this Book 14
3. Abbreviations 24
Chapter II. Metallation of Acetylenes 26
1. Monometallation of Acetylenes with a Terminal Triple Bond 26
2. Side and Subsequent Reactions 28
3. Dimetallated Acetylenes 29
4. Experiments (4.1 - 4.22) 30
Chapter .II Functionalization of Metallated Acetylenes with Alkyl Halides, a-Haloethers, Epoxides and Alkyl Orthoformates 52
1. Alkylation with Alkyl Halides. Scope and Limitations 52
2. Reaction of Metallated Acetylenes with Epoxides and Alkyl Orthoformates 53
3. Choice of the Counter Ion for Alkylation Reactions in Liquid Ammonia 54
4. Reaction of Metallated Acetylenes with a-Haloethers 54
5. Experiments (5.1 - 5.37) 55
Chapter IV Ethynylation and Alkynylation of Carbonyl Compounds 92
1. Survey of Laboratory Methods 92
2. Experiments (2.1 - 2.14) 93
Chapter V. Carboxylation, Alkylation and Related Reactions 110
1. Introduction 110
2. Carboxylations 110
3. Alkylations and Related Reactions 111
4. Experiments (4.1-4.13) 113
Chapter VI Silylation, Stannylation and Phosphorylation 126
1. Introduction 126
2. Reaction Conditions for Silylation, Stannylation and Phosphorylation 126
3. The Choice of Reaction Conditions for Silylations 127
4. Experiments (4.1 - 4.17) 127
Chapter VII Sulfenylations and Related Reactions 142
1. Methods for the Direct Introduction of Sulfur, Selenium and Tellurium 142
2. Experiments (2.1 -2.12) 143
3. Other Preparative Methods 153
Chapter VIII Halogenation and Cyanation 156
1. Methods for the Direct Introduction of Halogen and Cyano Groups 156
2. Other Preparative Methods 157
3. Choice of the Method and Reaction Conditions 159
4. Experiments (4.1 - 4.8) 160
Chapter IX Introduction of the Triple Bond by Elimination andAddition-Elimination Reactions 172
1. S urvey of Methods 172
2. Experiments (2.1 - 2.41) 178
Chapter X Couplings of Acetylenes Assisted by Copper and Palladium Compounds 222
1. Mannich Reactions - General Introduction 222
2. Cadiot-Chodkiewicz Couplings - General Introduction 225
3. Pd°-Catalysed Couplings of Acetylenes with sp2-Halogen CompoundsGeneral Introduction 227
4. Oxidative Couplings of Acetylenic Compounds - General Introduction 232
5. Copper(I)-catalysed Couplings of Acetylenes with Allylic and Propargylic Halides and Tosylates - General Introduction 236
6. Preparation of Alkynenitriles from 1-Bromoalkynes and Copper(I) Cyanide Experiment 241
Chapter XI Base-Promoted Interconversions of Acetylenes 244
1. Base-Catalysed Isomerizations 244
2. Isomerizations via Metallated Intermediates 244
3. Experiments (3.1 - 3.11) 246
Chapter .II Miscellaneous Preparations of Acetylenic Derivatives 260
1. Halogen Compounds, Sulfonates, Sulfonates and Acetates 260
2. Ethers, Sulfides and Thiols 272
3. Amines, Isothiocyanates, Nitriles 285
4. Ketones, Sulfoxides, Sulfones 294
5. Partial Reduction of the Triple Bond in Diyne Systems 296
6. Removal of Protecting Groups 301
Instructions for Searching 304
List of Selected Compounds 305
Type-Compound-Method Index 307
References 326