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Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 47b (eBook)

Alkenes

Armin de Meijere (Herausgeber)

eBook Download: PDF | EPUB

2014 | 1. Auflage
670 Seiten
Thieme (Verlag)
978-3-13-172281-2 (ISBN)

Lese- und Medienproben

Ebook-Leseprobe (PDF)

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Science of Synthesis – Volume 47b: Alkenes 1
Title page 3
Imprint 5
Preface 6
Volume Editor’s Preface 8
Overview 10
Table of Contents 12
47.1 Product Class 1: Alkenes 24
47.1.3 Synthesis by Pericyclic Reactions 24
47.1.3.1 Diels--Alder Reactions 24
47.1.3.1.1 Thermal Diels--Alder Reactions 42
47.1.3.1.1.1 Method 1: Reactions of Carbonyl Dienophiles 42
47.1.3.1.1.1.1 Variation 1: Synthesis of Cyclohexenecarbaldehydes 42
47.1.3.1.1.1.2 Variation 2: Synthesis of Acetylcyclohexenes 48
47.1.3.1.1.1.3 Variation 3: Synthesis of Cyclohexenecarboxylic Acids and Alkyl Cyclohexenecarboxylates 54
47.1.3.1.1.1.4 Variation 4: Synthesis of Dialkyl Cyclohexenedicarboxylates 60
47.1.3.1.1.1.5 Variation 5: Synthesis of Cyclohexenecarboxylic Acids, Cyclohexene carbonyl Chlorides, Cyclohexenecarboxamides, and Cyclohexenyl Silyl Ketones 64
47.1.3.1.1.1.6 Variation 6: Synthesis of Cyclohexenes Fused to Carbo- and Heterocycles 67
47.1.3.1.1.1.7 Variation 7: Synthesis of Bridged Cyclohexenes 82
47.1.3.1.1.2 Method 2: Reactions of Other Vinyl Dienophiles 94
47.1.3.1.1.2.1 Variation 1: Synthesis of Nitrocyclohexenes 94
47.1.3.1.1.2.2 Variation 2: Synthesis of Cyclohexenylboranes 97
47.1.3.1.1.2.3 Variation 3: Synthesis of Cyclohexenecarbonitriles 101
47.1.3.1.1.2.4 Variation 4: Synthesis of Cyclohex-3-enyl Phenyl Sulfones 104
47.1.3.1.1.2.5 Variation 5: Synthesis of (Hydroxyalkyl)cyclohexenes 107
47.1.3.1.1.2.6 Variation 6: Synthesis of Cyclohexenes from Unusual Dienophiles 111
47.1.3.1.1.3 Method 3: Synthesis of Cyclohexenyl-Substituted Fischer Carbene Complexes 114
47.1.3.1.1.4 Method 4: Synthetic Applications of Diels--Alder Reactions 118
47.1.3.1.2 Catalyzed Diels--Alder Reactions in Conventional Organic Media 123
47.1.3.1.2.1 Method 1: Reactions Using Classic Lewis Acid Catalysts 125
47.1.3.1.2.2 Method 2: Reactions Using Chiral Lewis Acid Catalysts 134
47.1.3.1.2.3 Method 3: Reactions Using Brønsted Acid Catalysts 138
47.1.3.1.2.4 Method 4: Reactions Using Chiral Organocatalysts 142
47.1.3.1.2.5 Method 5: Lewis Acid Catalyzed Diels--Alder Reactions of Chiral Dienophiles or Dienes 145
47.1.3.1.2.5.1 Variation 1: With Chiral Dienophiles 145
47.1.3.1.2.5.2 Variation 2: With Chiral Dienes 150
47.1.3.1.2.6 Method 6: Reactions Using Heterogeneous Catalysts 152
47.1.3.1.3 Diels--Alder Reactions in Unconventional Media 157
47.1.3.1.3.1 Method 1: Reactions in Water 157
47.1.3.1.3.1.1 Variation 1: Without a Catalyst 157
47.1.3.1.3.1.2 Variation 2: With a Lewis Acid Catalyst 160
47.1.3.1.3.1.3 Variation 3: With Organocatalysts 163
47.1.3.1.3.1.4 Variation 4: In Supercritical Water 164
47.1.3.1.3.1.5 Variation 5: In Pseudo-Biological Systems or Promoted by Biocatalysts 165
47.1.3.1.3.2 Method 2: Reactions in Nonaqueous Solvents and Their Salt Solutions 167
47.1.3.1.3.3 Method 3: Reactions in Ionic Liquids 170
47.1.3.1.4 Diels--Alder Reactions Induced by Other Physical Means 175
47.1.3.1.4.1 Method 1: Diels--Alder Reactions Promoted by Microwave Irradiation 175
47.1.3.1.4.2 Method 2: Diels--Alder Reactions Promoted by High Pressure 178
47.1.3.1.4.3 Method 3: Ultrasound-Assisted Diels--Alder Reactions 182
47.1.3.1.4.4 Method 4: Photoinduced Diels--Alder Reactions 185
47.1.3.2 Ene Reactions 200
47.1.3.2.1 Method 1: Thermal Ene Reactions 202
47.1.3.2.1.1 Variation 1: Intermolecular Ene Reactions 202
47.1.3.2.1.2 Variation 2: Reactions of 1,n-Dienes 203
47.1.3.2.2 Method 2: Metallo-Ene Reactions of Allylmetal Species 206
47.1.3.2.2.1 Variation 1: Reactions Using Alkenes as Enophiles, Followed by Protonolysis 206
47.1.3.2.2.2 Variation 2: Reactions Using Vinylmetals as Enophiles, Followed by Protonolysis 209
47.1.3.2.3 Method 3: Metal-Catalyzed Metallo-Ene Reactions 210
47.1.3.2.3.1 Variation 1: Palladium-Catalyzed Metallo-Ene Reactions Terminated by Transmetalation and Protonation 210
47.1.3.2.3.2 Variation 2: Palladium-Catalyzed Metallo-Ene Reactions Terminated by Hydride Capture 211
47.1.3.2.4 Method 4: Metal-Catalyzed Rearrangements 212
47.1.3.2.5 Method 5: Retro-Ene Reactions of All-Carbon Ene Adducts 213
47.1.3.2.5.1 Variation 1: Reactions of Homoallylic Alcohols 213
47.1.3.2.5.2 Variation 2: Reactions of Allyldiazenes 213
47.1.3.2.5.3 Variation 3: Reactions of Alk-2-enesulfinic Acid Derivatives 214
47.1.3.3 Synthesis by Electrocyclic Reactions 218
47.1.3.3.1 Method 1: Rearrangement of 4p-Electron Systems 218
47.1.3.3.1.1 Variation 1: Rearrangement of Acyclic 1,3-Dienes 218
47.1.3.3.1.2 Variation 2: Rearrangement of Cyclic 1,3-Dienes 219
47.1.3.3.1.3 Variation 3: Rearrangement of 1,2-Dimethylene-Substituted Cycloalkanes 221
47.1.3.3.1.4 Variation 4: Rearrangement of 1,2-Dimethylene-Substituted Heterocycles 222
47.1.3.3.2 Method 2: Rearrangement of 2p-Electron Systems 223
47.1.3.3.2.1 Variation 1: Solvolysis of Chlorocyclopropanes 223
47.1.3.3.2.2 Variation 2: Solvolysis of Cyclopropyl 4-Toluenesulfonates 225
47.1.3.3.3 Method 3: Cope Rearrangement 226
47.1.3.3.3.1 Variation 1: Rearrangement of Acyclic 1,5-Dienes 226
47.1.3.3.3.2 Variation 2: Rearrangement of Cyclic 1,5-Dienes 228
47.1.3.3.3.3 Variation 3: Rearrangement of 1,2-Divinylcycloalkanes 229
47.1.4 Synthesis by Elimination Reactions 234
47.1.4.1 Method 1: Synthesis by Decarbonylative Elimination 234
47.1.4.1.1 Variation 1: Oxidative Decarboxylation of Carboxylic Acids 234
47.1.4.1.2 Variation 2: Oxidative Decarboxylation of Acid Anhydrides 235
47.1.4.1.3 Variation 3: Decarbonylation of Acid Halides and Aldehydes 236
47.1.4.1.4 Variation 4: Decarbonylative Reactions of ß,.-Unsaturated Acids 236
47.1.4.1.5 Variation 5: Decarbonylative Elimination from ß-Halo- and ß-Hydroxycarboxylic Acids 237
47.1.4.1.6 Variation 6: Fragmentation of ß-Lactones 239
47.1.4.1.7 Variation 7: Fragmentation of 1,3-Diketones 240
47.1.4.1.8 Variation 8: Grob Fragmentation 241
47.1.4.2 Method 2: Oxidative Decarboxylation of Dicarboxylic Acid Derivatives 241
47.1.4.2.1 Variation 1: Oxidative Decarboxylation of 1,2-Dicarboxylic Acid Derivatives 241
47.1.4.2.2 Variation 2: Oxidative Decarboxylation of 1,3-Dicarboxylic Acids 243
47.1.4.3 Method 3: Base-Catalyzed and Solvolytic HX Elimination 243
47.1.4.3.1 Variation 1: Elimination from Alkyl Halides 243
47.1.4.3.2 Variation 2: Elimination from Ethers and Sulfides 251
47.1.4.3.3 Variation 3: Elimination from Metal Alkoxides 253
47.1.4.3.4 Variation 4: Elimination from Ammonium Salts 255
47.1.4.3.5 Variation 5: Elimination from Sulfonium Salts 257
47.1.4.3.6 Variation 6: Solvolytic and Base-Catalyzed Elimination from 4-Toluenesulfonates and Other Sulfonates 258
47.1.4.4 Method 4: Acid-Catalyzed HX Elimination 262
47.1.4.4.1 Variation 1: Acid-Catalyzed Dehydration of Alcohols 262
47.1.4.4.2 Variation 2: Dehydration of Alcohols Using Lewis Acids and Heterogeneous Catalysts 266
47.1.4.4.3 Variation 3: Dehydration of Alcohols with Other Systems 270
47.1.4.5 Method 5: Pyrolytic HX Elimination 275
47.1.4.5.1 Variation 1: Pyrolysis of Alkyl Halides 275
47.1.4.5.2 Variation 2: Pyrolysis of Esters 276
47.1.4.5.3 Variation 3: Pyrolysis of Xanthates, Thiocarbamates, Thiophosphates, Arenesulfonates, Sulfamates, and Sulfuranes 279
47.1.4.5.4 Variation 4: Cope Elimination from N-Oxides 284
47.1.4.5.5 Variation 5: Thermolytic Elimination from Ammonium Hydroxides 287
47.1.4.5.6 Variation 6: Thermolytic Elimination from Phosphonium Salts 288
47.1.4.5.7 Variation 7: Thermolytic Elimination from Alkyl Selenoxides 289
47.1.4.5.8 Variation 8: Thermolytic Dehydration of Alcohols in Dimethyl Sulfoxide or Hexamethylphosphoric Triamide 290
47.1.4.6 Method 6: Reductive Elimination from Halohydrins and Their Esters or Ethers 292
47.1.4.6.1 Variation 1: Dehalogenation of Vicinal Dihalides 292
47.1.4.6.2 Variation 2: Elimination from Halohydrins 295
47.1.4.6.3 Variation 3: Elimination from Halohydrin Esters 296
47.1.4.6.4 Variation 4: Elimination from Halohydrin Ethers 297
47.1.4.6.5 Variation 5: Elimination from vic-Diols 299
47.1.4.6.6 Variation 6: Elimination from vic-Diol Disulfonates 301
47.1.4.7 Method 7: Reductive Elimination of X2 from Fragments of the Type CX2--CH2 303
47.1.4.7.1 Variation 1: Dehalogenation of Geminal Dihalides 303
47.1.4.7.2 Variation 2: Elimination of Nitrogen from Diazo Compounds 304
47.1.4.8 Method 8: Reductive Extrusions from Three- to Five-Membered Heterocycles 304
47.1.4.8.1 Variation 1: From Oxiranes 304
47.1.4.8.2 Variation 2: From Thiiranes and Thiirane 1,1-Dioxides 307
47.1.4.8.3 Variation 3: Ramberg--Bäcklund Reaction 310
47.1.4.8.4 Variation 4: From Aziridines 311
47.1.4.8.5 Variation 5: From 1,3-Dioxolane- and 1,3-Dithiolane-2-thiones 312
47.1.4.8.6 Variation 6: From 2-Alkoxy- and 2-(Dimethylamino)-1,3-dioxolanes 314
47.1.4.9 Method 9: Reactions of Ketone (Arylsulfonyl)hydrazones 316
47.1.4.9.1 Variation 1: The Bamford--Stevens Reaction 317
47.1.4.9.2 Variation 2: The Shapiro Reaction 323
47.1.4.9.3 Variation 3: Sequential Transformations Based on the Shapiro Reaction 329
47.1.4.10 Method 10: Dehydrogenation of CH2--CH2 Fragments 334
47.1.5 Synthesis from Alkynes by Addition Reactions 346
47.1.5.1 [2+2]-Cycloaddition Reactions 346
47.1.5.1.1 Method 1: Photochemical and Microwave-Assisted Reactions 346
47.1.5.1.1.1 Variation 1: From Diphenylacetylene 346
47.1.5.1.1.2 Variation 2: From Diynes, Triynes, and Vinylacetylene 347
47.1.5.1.1.3 Variation 3: Intramolecular Reactions 349
47.1.5.1.2 Method 2: Thermocatalytic Reactions 350
47.1.5.1.2.1 Variation 1: Lewis Acid Catalyzed [2+2] Cycloadditions 350
47.1.5.1.2.2 Variation 2: Reactions Catalyzed by Nickel, Ruthenium, and Cobalt Complexes 351
47.1.5.1.2.3 Variation 3: Zirconocene-Catalyzed Cyclobutene Formation 355
47.1.5.2 Hydrogenation Reactions 360
47.1.5.2.1 Method 1: Catalytic Hydrogenation 360
47.1.5.2.2 Method 2: Chemical Reduction 362
47.1.5.2.2.1 Variation 1: Reduction with Metals 362
47.1.5.2.2.2 Variation 2: Reduction by Hydrometalation--Protodemetalation 365
47.1.5.3 Hydrometalation and Subsequent Coupling Reactions 372
47.1.5.3.1 Method 1: syn-Hydrometalation Reactions of Alkynes Producing E-ß-Mono-, syn-a,ß-Di-, and anti-a,ß-Disubstituted Alkenylmetals 381
47.1.5.3.1.1 Variation 1: syn-Hydrometalation of Alkynes Involving Group 1, 2, 11, and 12 Metals 381
47.1.5.3.1.2 Variation 2: Hydroboration of Alkynes 382
47.1.5.3.1.3 Variation 3: Substitution of Boron in the Hydroboration Products with Hydrogen and Heteroatoms 384
47.1.5.3.1.4 Variation 4: C--C Bond-Forming Reactions That Are Unique to Organoboranes 386
47.1.5.3.1.5 Variation 5: Hydroalumination and Hydrozirconation of Alkynes 388
47.1.5.3.1.6 Variation 6: Substitution of the Metal in Alkenylaluminum and Alkenylzirconium Compounds with Hydrogen or Deuterium, Halogens, Other Heteroatoms, Metals, and Carbon 392
47.1.5.3.2 Method 2: anti-Hydrometalation Reactions of Alkynes Producing Z-ß-Mono- and anti-a,ß-Disubstituted Alkenylmetals 395
47.1.5.3.2.1 Variation 1: anti-Hydroalumination of Alkynes with Hydroaluminates 395
47.1.5.3.2.2 Variation 2: Other anti-Hydrometalation Reactions of Alkynes 396
47.1.5.3.2.3 Variation 3: Useful Alternatives to anti-Hydrometalation of Alkynes 396
47.1.5.3.3 Method 3: Palladium-Catalyzed Cross-Coupling Reactions of Alkenylmetals or Alkenyl Electrophiles Prepared by Alkyne Hydrometalation 398
47.1.5.3.3.1 Variation 1: 1,2-Disubstituted E-Alkenes via ß-Monosubstituted E-Alkenyl Derivatives 400
47.1.5.3.3.2 Variation 2: 1,2-Disubstituted E-Alkenes via ß-Monosubstituted E-Alkenyl Derivatives Preparable by Methods Other Than Hydrometalation 413
47.1.5.3.3.3 Variation 3: 1,2-Disubstituted Z-Alkenes via ß-Monosubstituted Z-Alkenyl Derivatives Preparable by Alkyne Hydrometalation, Ethyne Carbocupration, and Other Methods 416
47.1.5.3.3.4 Variation 4: Trisubstituted Alkenes via syn-a,ß-Disubstituted Alkenyl Derivatives Preparable by Alkyne syn-Hydrometalation and Other Methods 420
47.1.5.3.3.5 Variation 5: Trisubstituted Alkenes via anti-a,ß-Disubstituted Alkenyl Derivatives Prepared by Alkyne syn- or anti-Hydrometalation and Other Methods Not Involving Elementometalation 425
47.1.5.4 Carbometalation and Subsequent Coupling Reactions 434
47.1.5.4.1 Method 1: Syntheses of Trisubstituted Alkenes via Zirconium-Catalyzed syn-Carboalumination of Alkynes 441
47.1.5.4.2 Method 2: Syntheses of Trisubstituted Alkenes by Carbocupration of Alkynes 461
47.1.5.4.2.1 Variation 1: syn-Carbocupration of Alkynes 461
47.1.5.4.2.2 Variation 2: Copper-Catalyzed anti-Carbomagnesiation of Propargyl Alcohols 465
47.1.5.4.3 Method 3: Synthesis of Trisubstituted Alkenes via syn-Haloboration of Alkynes 466
47.1.5.4.4 Method 4: Synthesis of Trisubstituted Alkenes via ß,ß-Disubstituted Alkenyl Derivatives Prepared by Miscellaneous Other Methods 470
47.1.5.4.5 Method 5: Synthesis of Tetrasubstituted Alkenes via Trisubstituted Alkenyl Derivatives 473
47.1.6 Synthesis from Arenes and Polyenes by Addition Reactions 480
47.1.6.1 Synthesis from Arenes 480
47.1.6.1.1 Method 1: Reduction by Metals in Liquid Ammonia 480
47.1.6.1.1.1 Variation 1: Reduction by Lithium and Added Ethanol 480
47.1.6.1.1.2 Variation 2: Reduction by Sodium and Added Ethanol 481
47.1.6.1.1.3 Variation 3: Reduction by Potassium and Added tert-Butyl Alcohol 481
47.1.6.1.1.4 Variation 4: Reduction by Calcium 481
47.1.6.1.2 Method 2: Reduction by Lithium and Alkylamines 482
47.1.6.1.2.1 Variation 1: Reduction in Methylamine or Ethylamine 482
47.1.6.1.2.2 Variation 2: Reduction in Ethylenediamine 482
47.1.6.1.2.3 Variation 3: Reduction in Mixed-Amine Systems 482
47.1.6.1.3 Method 3: Electrochemical Reduction in Methylamine 483
47.1.6.1.4 Method 4: Reduction by Sodium and tert-Butyl Alcohol 483
47.1.6.2 Synthesis from 1,2-Dienes (Allenes) 483
47.1.6.2.1 Method 1: Reduction by Addition of Hydrogen 483
47.1.6.2.1.1 Variation 1: Catalytic Hydrogenation 483
47.1.6.2.1.2 Variation 2: Transfer Hydrogenation Using Ammonium Formate 485
47.1.6.2.1.3 Variation 3: Reduction by Lithium or Sodium in Liquid Ammonia 485
47.1.6.2.1.4 Variation 4: Reduction by Sodium and Ethanol 485
47.1.6.2.1.5 Variation 5: Reduction by the Zinc--Copper Couple 486
47.1.6.2.1.6 Variation 6: Reduction by Diimide 486
47.1.6.2.1.7 Variation 7: Reduction by Red Phosphorus and Hydriodic Acid 486
47.1.6.2.1.8 Variation 8: Reduction by Borane 487
47.1.6.2.1.9 Variation 9: Reduction by Aluminum Hydrides 487
47.1.6.2.1.10 Variation 10: Reduction by Baker's Yeast 487
47.1.6.2.1.11 Variation 11: Miscellaneous Variations 487
47.1.6.2.2 Method 2: Synthesis by Hydrocarbonation (Addition of Carbon and Hydrogen) 487
47.1.6.2.2.1 Variation 1: Hydrocarbonation Using a Grignard Reagent 488
47.1.6.2.2.2 Variation 2: Hydrocarbonation Using Arylboronates 488
47.1.6.2.2.3 Variation 3: Hydrocarbonation Using Stabilized Carbanions 488
47.1.6.2.2.4 Variation 4: Hydrocarbonation by Hydrozirconation Followed by Zinc-Mediated Claisen Rearrangement 489
47.1.6.2.2.5 Variation 5: Hydrocarbonation by Reductive Coupling to Carbonyl Compounds 490
47.1.6.3 Synthesis from 1,3-Dienes or Fully Conjugated Polyenes 491
47.1.6.3.1 Synthesis by Addition of Hydrogen 491
47.1.6.3.1.1 Method 1: Catalytic Hydrogenation 491
47.1.6.3.1.1.1 Variation 1: Hydrogenation Using Chromium or Molybdenum Catalysts 491
47.1.6.3.1.1.2 Variation 2: Hydrogenation Using Nickel Catalysts 492
47.1.6.3.1.1.3 Variation 3: Hydrogenation Using Palladium Catalysts 493
47.1.6.3.1.1.4 Variation 4: Hydrogenation Using Platinum Catalysts 494
47.1.6.3.1.1.5 Variation 5: Hydrogenation Using Other Metal Catalysts 495
47.1.6.3.1.2 Method 2: Dissolving Metal Reduction 496
47.1.6.3.1.2.1 Variation 1: Reduction by Lithium and Ammonia 496
47.1.6.3.1.2.2 Variation 2: Reduction by Sodium and Ammonia 496
47.1.6.3.1.2.3 Variation 3: Reduction by Sodium Amalgam 497
47.1.6.3.1.2.4 Variation 4: Reduction by Sodium and an Alcohol 498
47.1.6.3.1.2.5 Variation 5: Reduction by Magnesium 499
47.1.6.3.1.2.6 Variation 6: Reduction by Aluminum Amalgam 499
47.1.6.3.1.2.7 Variation 7: Reduction by Zinc and Acetic Acid 499
47.1.6.3.1.3 Method 3: Reduction by Sodium Borohydride with Iodine or Disodium Tetracyanonickelate 500
47.1.6.3.1.4 Method 4: Reduction by Diisobutylaluminum Hydride 500
47.1.6.3.1.5 Method 5: Reduction by Platinum-Catalyzed Hydrosilylation 501
47.1.6.3.1.6 Method 6: Reduction by Diimide 501
47.1.6.3.1.7 Method 7: Reduction by Sodium Dithionite 502
47.1.6.3.1.8 Method 8: Reduction by Zirconocene and Hydrochloric Acid 503
47.1.6.3.1.9 Method 9: Reduction by Vanadium(II) and Pyrocatechol 503
47.1.6.3.1.10 Method 10: Reduction by Samarium and Water 503
47.1.6.3.1.11 Method 11: Electrochemical Reduction 504
47.1.6.3.1.12 Method 12: Reduction by Nicotinamide Adenine Dinucleotide Model Dihydropyridines 504
47.1.6.3.1.13 Method 13: Reduction by Yeasts 504
47.1.6.3.2 Synthesis by Hydrocarbonation (Addition of Carbon and Hydrogen) 505
47.1.6.3.2.1 Method 1: Hydrocarbonation Using Alkyllithium Reagents 505
47.1.6.3.2.2 Method 2: Hydrocarbonation Using Alkylsodium Reagents 506
47.1.6.3.2.3 Method 3: Hydrocarbonation Using Organometallic Reagents 507
47.1.6.3.2.4 Method 4: Hydrocarbonation Using Nitroalkane Anions 509
47.1.6.3.2.5 Method 5: Hydrocarbonation Using Stabilized Carbanions 510
47.1.6.3.2.6 Method 6: Hydrocarbonation by Reductive Coupling to Carbonyl Compounds, Imines, or Alkenes 512
47.1.6.3.3 Synthesis by Carbonation (Formation of Two C--C Bonds) 514
47.1.6.3.3.1 Method 1: Carbonation Using an Alkyl- or Aryllithium and a Haloalkane 514
47.1.6.3.3.2 Method 2: Carbonation Using a Grignard Reagent Followed by Carbon Dioxide 514
47.1.6.3.3.3 Method 3: Carbonation Using a Nickel-Catalyst with Trimethylborane or Dimethylzinc and an Aldehyde 515
47.1.6.3.3.4 Method 4: Carbonation Using an Alkylcopper Reagent Followed by a Carbonyl or Haloalkane Electrophile 515
47.1.6.3.3.5 Method 5: Carbonation Using an Acyl(carbonyl)cobalt Reagent and a Stabilized Carbanion 516
47.1.6.3.4 Addition Across Two Molecules of a 1,3-Diene 517
47.1.6.3.4.1 Method 1: Hydrocarbonation Using Nitroalkane Anions 517
47.1.6.3.4.2 Method 2: Hydrocarbonation Using Stabilized Carbanions 518
47.1.6.3.4.3 Method 3: Hydrocarbonation Using Reductive Coupling to Imines and Alkenes 518
47.1.6.3.4.4 Method 4: Carbonation Using Alkyl Radicals 518
47.1.6.3.4.5 Method 5: Addition of Ammonia and Amines 519
47.1.6.3.4.6 Method 6: Addition of Alcohols, Phenols, or Carboxylic Acids 519
47.1.6.3.4.7 Method 7: Addition of Arenesulfinic Acids 520
47.1.6.4 Synthesis from 1,4-Dienes, 1,5-Dienes, or Higher Dienes 520
47.1.6.4.1 Method 1: Catalytic Hydrogenation 520
47.1.6.4.1.1 Variation 1: Hydrogenation Using Nickel Catalysts 520
47.1.6.4.1.2 Variation 2: Hydrogenation Using Palladium Catalysts 521
47.1.6.4.1.3 Variation 3: Hydrogenation Using Platinum Catalysts 521
47.1.6.4.1.4 Variation 4: Hydrogenation Using Other Metal Catalysts 522
47.1.6.4.2 Method 2: Reduction by Magnesium 523
47.1.6.4.3 Method 3: Reduction by Diimide 523
47.1.6.4.4 Method 4: Reduction by Sodium Hydrazide/Hydrazine 524
47.1.6.4.5 Method 5: Reduction by Nicotinamide Adenine Dinucleotide Model Dihydropyridines 524
47.1.7 Synthesis by Isomerization 530
47.1.7.1 Method 1: Rearrangement from Terminal to Internal Alkenes 530
47.1.7.1.1 Variation 1: Using Ruthenium Complexes 530
47.1.7.1.2 Variation 2: Using Rhodium Catalysts 532
47.1.7.1.3 Variation 3: Using Palladium Complexes 533
47.1.7.1.4 Variation 4: Using Diphenyl Disulfone 534
47.1.7.2 Method 2: Rearrangement from Internal to Terminal Alkenes 535
47.1.7.3 Method 3: Rearrangement of Z- and E-Alkenes 537
47.1.7.3.1 Variation 1: Conversion of an E-Alkene into a Z-Alkene 538
47.1.7.3.2 Variation 2: Conversion of a Z-Alkene into an E-Alkene 539
47.1.7.4 Method 4: Allylic Rearrangement 540
47.1.7.4.1 Variation 1: Of Alcohols and Ethers 540
47.1.7.4.2 Variation 2: Of Esters and Imidates 545
47.1.7.4.3 Variation 3: Of Sulfoxides, Selenoxides, Sulfones, and Related Compounds 547
47.1.7.4.4 Variation 4: Of Azides 549
47.1.7.5 Method 5: Rearrangement of Vinylcyclopropanes 550
47.1.7.5.1 Variation 1: Under Thermal Conditions 551
47.1.7.5.2 Variation 2: Under Photochemical Conditions 551
47.1.7.5.3 Variation 3: Under Transition-Metal Catalysis 553
47.1.8 Synthesis from Other Alkenes without Isomerization 558
47.1.8.1 Method 1: Electrophilic Substitution 558
47.1.8.1.1 Variation 1: Acylation Reactions 558
47.1.8.1.2 Variation 2: Reactions of Vinylsilanes and Vinylstannanes 559
47.1.8.2 Method 2: Nucleophilic Substitution 562
47.1.8.2.1 Variation 1: Reactions with Carbon Nucleophiles 562
47.1.8.2.2 Variation 2: Reactions with Heteroatom Nucleophiles 563
47.1.8.3 Method 3: Alkylation of Organometallic Compounds 565
47.1.8.3.1 Variation 1: Reactions of Organolithium Compounds 566
47.1.8.3.2 Variation 2: Reactions of Organomagnesium Compounds 568
47.1.8.3.3 Variation 3: Reactions of Organocopper Compounds 570
47.2 Product Class 2: Cyclopropenes 574
47.2.1 Synthesis of Product Class 2 574
47.2.1.1 Method 1: Synthesis by Ring Closure with Formation of Two C--C Bonds 574
47.2.1.2 Method 2: Synthesis by Ring Closure with Formation of One C--C Bond 576
47.2.1.2.1 Variation 1: Dehydrohalogenation of Allylic Halides 576
47.2.1.2.2 Variation 2: Cyclizing Insertions of Methylenecarbenes (Vinylidenes) or Related Species 577
47.2.1.2.3 Variation 3: 1,3-Elimination from Propenes 577
47.2.1.2.4 Variation 4: By Formation of the C==C Bond 578
47.2.1.3 Method 3: Synthesis by Ring Contraction 578
47.2.1.4 Method 4: Synthesis by 1,2-Elimination 579
47.2.1.4.1 Variation 1: Dehydrohalogenation 579
47.2.1.4.2 Variation 2: Dehalogenation 583
47.2.1.4.3 Variation 3: Dehalosilylation 586
47.2.1.4.4 Variation 4: Dehydroxysilylation 587
47.2.1.5 Method 5: Synthesis by Rearrangement of Methylenecyclopropanes 588
47.2.1.6 Method 6: Synthesis from Other Cyclopropenes 589
47.2.1.6.1 Variation 1: By Alkylation of a Carbon Nucleophile 589
47.2.1.6.2 Variation 2: By Alkylation with an Electrophilic Reagent 590
47.2.1.6.3 Variation 3: By Ene Reactions 590
47.2.1.7 Method 7: Miscellaneous Methods 593
47.3 Product Class 3: Nonconjugated Di-, Tri-, and Oligoenes 598
47.3.1 Synthesis of Product Class 3 598
47.3.1.1 Synthesis with C--C Bond Formation 598
47.3.1.1.1 Method 1: Wittig-Type Reactions 598
47.3.1.1.2 Method 2: Coupling Reactions with Organometallic Compounds 601
47.3.1.1.2.1 Variation 1: With Organomagnesium Compounds 601
47.3.1.1.2.2 Variation 2: With Organoboron Compounds 603
47.3.1.1.2.3 Variation 3: With Organoaluminum and Organoindium Compounds 604
47.3.1.1.2.4 Variation 4: With Organosilicon and Organotin Compounds 605
47.3.1.1.2.5 Variation 5: With Other Organometallic Compounds 609
47.3.1.1.3 Method 3: Dimerization and Oligomerization Reactions 613
47.3.1.2 Synthesis by Elimination 613
47.3.1.2.1 Method 1: Synthesis from Cyclopropylcarbinols 613
47.3.1.2.2 Method 2: Synthesis from Iodohydrin Derivatives 614
47.3.1.2.3 Method 3: Hydroboration--Elimination of Enamines 615
47.3.1.3 Synthesis by Reduction 615
47.3.1.3.1 Method 1: Catalytic Hydrogenation 615
47.3.1.3.2 Method 2: Chemical Reduction 616
47.3.1.3.3 Method 3: Electrochemical Reduction 617
Keyword Index 620
Author Index 658
Abbreviations 688

Erscheint lt. Verlag	14.5.2014
Reihe/Serie	Science of Synthesis
Verlagsort	Stuttgart
Sprache	englisch
Themenwelt	Naturwissenschaften ► Chemie ► Organische Chemie
Themenwelt	Technik
Schlagworte	Alkenes • Chemie • Chemische Synthese • chemistry of organic compound • chemistry organic reaction • chemistry reference work • C HEMISTRY REFERENCE WORK • chemistry synthetic methods • compound functional group • compound organic synthesis • compounds with all-carbon functions • cycloalkenes • ethene • ETH ENE • hydrocarbon alkenes • isomeric butenes • Mechanism • methods in organic synthesis • methods peptide synthesis • Organic Chemistry • organic chemistry functional groups • organic chemistry reactions • organic chemistry review • organic chemistry synthesis • ORGANIC CHEM ISTRY SYNTHESIS • organic method • organic reaction • organic reaction mechanism • ORGANI C REACTION MECHANISM • Organic Syntheses • organic synthesis • organic synthesis reference work • Organisch-chemische Synthese • Organische Chemie • Peptide synthesis • Practical • practical organic chemistry • propene • Reactions • reference work • Review • review organic synthesis • review synthetic methods • REVIEW SYNTHE TIC METHODS • Synthese • Synthetic chemistry • Synthetic Methods • Synthetic Organic Chemistry • synthetic transformation
ISBN-10	3-13-172281-9 / 3131722819
ISBN-13	978-3-13-172281-2 / 9783131722812

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