Best Synthetic Methods: Acetylenes, Allenes and Cumulenes (Best Synthetic Methods)

✍ Scribed by Lambert Brandsma

• Year: 2004
• Tongue: English
• Leaves: 503
• Edition: 1
• Category: Library

✦ Synopsis

There is a vast and often bewildering array of synthetic methods and reagents available to organic chemists today. The Best Synthetic Methods series allows any scientist who is interested in the chemical transformations of molecules to choose between all the alternatives and assess their real advantages and limitations. With the emphasis on laboratory use, these volumes represent a comprehensive and practical guide to modern synthetic organic chemistry.This book is the product of the author's many years practical experience and reading of the original literature. It contains a valuable distillation and critical evaluation of the Best Synthetic Methods for the formation and reaction of molecules containing carbon-carbon triple bonds or cumulative carbon-carbon double bonds. A brief review of each area is provided, but the emphasis in all cases is on describing efficient practical methods to effect the transformations described. The reader can therefore use this book to rapidly review and select the best methods of performing a synthetic conversion to create or modify a molecule containing an acetylene, allene or cumulene functionality. In addition, the documentation of a large number of experimental recipes enables the user to synthesise an unsaturated molecule without the need to access to the original literature. - Reviews and evaluates the various methods for the formation and reaction of acetylenes, cumulenes and allenes. - Provides detailed practical experimental for many important reactions. - General tips and analytical data are provided from the author's own extensive research in this area.

✦ Table of Contents

Front Cover......Page 1
Synthesis of Acetylenes, Allenes and Cumulenes: Methods and Techniques......Page 4
Copyright Page......Page 5
Preface......Page 6
Contents......Page 8
1.2 Reactions in liquid ammonia......Page 34
1.3 Some practical hints......Page 36
2.1 Solvents......Page 44
2.2 Reagents......Page 46
2.3 Experimental section......Page 49
References......Page 56
3.1 Deprotonation of acetylenes with a terminal triple bond......Page 58
3.2 Side reactions......Page 60
3.3 In situ generation of metallated acetylenes and cumulenes by elimination reactions......Page 61
3.4 1,3-Dimetallated acetylenes......Page 63
3.5 Metallation of allenes and acetylenes with a non-terminal triple bond......Page 64
3.6 Addition of organolithium compounds and lithium alanate to compounds with an enyne or diyne system......Page 67
3.7 Formation of alkali acetylides from acetylenes with a non-terminal triple bond and from allenes by the action of strong bases......Page 68
3.8 Generation of metallated acetylenes by successive dehalogenations or by successive dehydrohalogenation and dehalogenation......Page 69
3.9 Experimental section......Page 71
3.10 Replacement of the lithium by other metals and application in synthesis......Page 113
References......Page 114
4.1 Alkylation with alkyl halides......Page 118
4.2 Reaction with oxiranes and oxetanes......Page 121
4.3 Reaction of metallated acetylenes and allenes with a-haloethers......Page 122
4.5 Experimental section......Page 123
References......Page 150
5.1 Survey of laboratory methods......Page 152
5.2 Experimental section......Page 154
References......Page 166
6.1 Introduction......Page 168
6.2 Reactions with heterocumulenes......Page 171
6.3 Acylation reactions......Page 172
6.4 Experimental section......Page 175
References......Page 191
7.1 Introduction......Page 194
7.2 Experimental section......Page 195
References......Page 206
8.1 Methods for the direct introduction of sulphur, selenium and tellurium......Page 208
8.2 Experimental section......Page 210
References......Page 221
9.1 Methods for the direct introduction of halogen......Page 224
9.2 Experimental section......Page 225
References......Page 235
10.1 Survey of methods......Page 236
10.2 Experimental section......Page 239
References......Page 260
11.1 Introduction......Page 262
11.2 Experimental section......Page 263
References......Page 267
12.1 Nucleophilic 1,1-substitution on sp-carbon......Page 268
12.2 Nucleophilic 1,3-substitution on sp- and sp2-carbon......Page 269
12.3 Electrophilic 1,3-substitutions......Page 270
12.4 Experimental section......Page 274
References......Page 297
13.1 Introduction......Page 300
13.2 Experimental section......Page 301
References......Page 305
14.1 Introduction......Page 306
14.2 Experimental section......Page 309
References......Page 312
15.1 Methods, scope and limitations......Page 314
15.2 Experimental section......Page 316
References......Page 324
16.1 Introduction......Page 326
16.2 Scope and limitations......Page 327
16.3 Relative rates of coupling......Page 331
16.4 Regiochemistry......Page 332
16.5 Synthetic applications of the cross-coupling reactions with acetylenes......Page 333
16.6 Practical aspects of the coupling reactions......Page 334
16.7 Experimental section......Page 337
References......Page 350
17.1 Introduction......Page 352
17.2 Experimental section......Page 353
References......Page 373
18.1 2,3-Sigmatropic rearrangements......Page 374
18.2 3,3-Sigmatropic rearrangements......Page 375
18.3 Experimental section......Page 376
References......Page 384
19.1 Elimination reactions resulting in additional unsaturation......Page 386
19.2 Removal of protecting groups......Page 392
19.3 Partial reductions of conjugated systems of triple bonds......Page 395
References......Page 400
20.1 Acetylenic halogen compounds......Page 402
20.2 Acetylenic amino and imino compounds......Page 414
20.3 Acetylenic and allenic nitriles, thiocyanates and isothiocyanates......Page 423
20.4 Acetylenic aldehydes, ketones and carboxylic acids......Page 428
20.5 Acetylenic esters, dithioesters and carboxamides......Page 430
20.6 Ethers......Page 435
20.7 Acetylenic sulphides and thiols......Page 445
20.8 Acetylenic and allenicsulphoxides, sulphones, sulphinamides and sulphonamides......Page 450
20.9 Dimetallated acetylenic compounds and their functionalisation......Page 453
20.10 Copper(I) bromide-catalysed formation of 2-propargylhetarenes......Page 456
References......Page 457
Appendix A: 1H- and 13C-NMR Chemical Shifts of Acetylenic, Allenic and Cumulenic Compounds......Page 460
Appendix B: Class-Compound-Method Index......Page 464
Appendix C: Complementary Subject Index......Page 488