Comprehensive Organic Functional Group Transformations II: v. 1(Carbon with No Attached Heteroatoms)

Cover Page......Page 1
Book Info......Page 2
Editors-in-Chief......Page 3
Editor of Volume 2......Page 5
Editor of Volume 4......Page 6
Editor of Volume 6......Page 7
Preface......Page 8
Introduction to Volume 1......Page 9
Explanation of the reference system......Page 10
Journal Abbreviations......Page 11
Techniques/Conditions......Page 13
Reagents, Solvents, etc.......Page 14
Part I: Tetracoordinated Carbon with No Attached Heteroatoms......Page 17
Part II: Tricoordinated Carbon with No Attached Heteroatoms......Page 18
Part III: Dicoordinate and Monocoordinate Carbon with No Attached Heteroatoms......Page 19
General Methods......Page 20
Reduction of Fluoroalkanes......Page 21
Reduction of Chloroalkanes......Page 22
Reduction of Bromoalkanes......Page 26
Reduction of Iodoalkanes......Page 29
General Methods......Page 31
Reduction of C-OH bonds......Page 32
Reduction of oxiranes......Page 33
Reduction of other ethers......Page 34
Reduction of thionoethers......Page 35
Reduction of aldehydes......Page 36
Reduction of ketones......Page 37
Reduction of C(=O)X to CH3......Page 38
Reduction of C(OX)n Systems......Page 39
Reduction of C-SX Bonds......Page 40
Reduction of C(SX)n Systems......Page 41
Reduction of C-Se Systems......Page 42
Reduction of C-Te Systems......Page 43
References......Page 44
Biographical sketch......Page 49
1.02 One or More C-H Bond(s) Formed by Substitution: Reduction of Carbon-Nitrogen, -Phosphorus, -Arsenic, -Antimony, -Bismuth, -Carbon, -Boron, and -Metal Bonds......Page 50
Reductive cleavage of sulfonimides......Page 51
Direct reduction of amines or ammonium salts......Page 52
Deamination using diazenes as intermediates......Page 53
Reductive cleavage of nitro groups......Page 54
Reductive cleavage of isonitrile groups......Page 56
Reductive cleavage of azido groups......Page 57
Use of palladium-mediated hydrogenolysis......Page 58
Use of single electron-transfer reagents......Page 59
Reduction of tosylhydrazones......Page 60
Reduction of C=N-NR1R2 systems where R1 or R2 is alkyl, acyl, aryl, or hydrogen......Page 62
Reduction of N-alkylimine type systems......Page 64
Reduction of diazo compounds......Page 65
Reduction of C-N Triple Bonds to the Methyl Group......Page 66
Reduction of nitriles using hydrogenolysis conditions......Page 67
Cleavage of C-P bonds under basic conditions......Page 68
Cleavage of C-P bonds with hydride......Page 70
Reduction of C-Sb Bonds......Page 71
Use of dissolving metals......Page 72
Miscellaneous methods for reductive decyanation......Page 73
Reductive cleavage of cyclopropylketones......Page 74
Reductive cleavage of other constrained cycloalkanes......Page 75
Barton reductive decarboxylation of carboxylic acids......Page 76
Metal-mediated decarbonylation of aldehydes......Page 77
Reductive cleavage of nonenolizables ketones......Page 78
Thermal decarboxylation of disubstituted malonic acids......Page 79
Use of other nucleophiles......Page 80
Metal-mediated decarboxylation of activated acids and esters......Page 81
Cleavage of carbon-boron bonds under acidic conditions......Page 82
Cleavage of carbon-boron bonds with base......Page 83
Cleavage by base......Page 84
Reduction of Carbon-Metal Bonds to Carbon-Hydrogen Bonds......Page 86
Metal hydride demercuration......Page 87
References......Page 90
Biographical sketch......Page 96
General Methods for Alkene Reduction......Page 98
Reduction of Alkyl-substituted Alkenes......Page 104
Reduction of Alkenyl-, Aryl-, Heteroaryl-, and Alkynyl-substituted Alkenes......Page 106
Reduction of Heteroalkyl-substituted Alkenes......Page 110
Reduction of Remotely Substituted Alkenes......Page 114
Heterogeneous Hydrogenation......Page 118
Homogeneous Hydrogenation of Arenes......Page 125
Dissolving Metal Reductions......Page 126
Hydride Reductions......Page 128
Reduction of Alkynes and Allenes......Page 129
References......Page 131
Biographical sketch......Page 138
1.04 One or More CC Bond(s) Formed by Substitution: Substitution of Halogen......Page 140
Group I Metals (Li, K)......Page 141
Metallation through hydrogen abstraction by lithiated or potassium bases......Page 142
Selenium-lithium exchange......Page 143
Carbolithiation of aromatic rings......Page 144
Reactivity of propargyllithiums......Page 145
Metallation by lateral hydrogen abstraction with lithiated bases or via tin-lithium transmetallation......Page 146
Lateral lithiation on arene chromium complexes......Page 149
Competition between ortho- versus benzylic lithiation......Page 150
Carbolithiation of styrene systems......Page 151
Reduction of dioxanes or ethers......Page 152
Alkylation of organobariums......Page 153
Carbocupration of alkenes......Page 154
Zinc insertion into carbon-halogen bonds......Page 155
Boron-zinc transmetallation......Page 156
Carbozincation of alkenes......Page 157
Asymmetric allylation of organozinc reagents......Page 158
Transmetallation of organomagnesiums......Page 159
Transmetallation of organosamariums......Page 160
Suzuki-coupling process......Page 161
Stille coupling......Page 162
Ni(0)-Catalyzed couplings......Page 163
Alkylation of organomanganese compounds......Page 164
Outline placeholder......Page 0
Lithium ketone enolates......Page 165
Reactivity of silyl enol ethers......Page 166
Alkylation of manganese(II) enolates......Page 168
alpha-Alkylation of imines......Page 169
alpha-Alkylation of nitriles......Page 170
Diastereoselective alkylations......Page 171
Intermolecular conjugate additions......Page 172
Alkylation of lactone enolates......Page 173
alpha-Alkylation of oxazolines......Page 174
alpha-Alkylation of amides and lactams......Page 175
Introduction of chirality from chiral auxiliaries......Page 176
Oxygen-stabilized Carbanions......Page 179
Metallation by tin-lithium exchange......Page 180
Alkylation of dipole-stabilized anions......Page 181
alpha-Alkylation of 1-oxysubstituted allyllithiums......Page 184
Lithiation by proton abstraction......Page 185
Lithium-selenium exchange......Page 186
Alkylation of alpha-lithio sulfides-carbolithiation of vinyl sulfides......Page 187
Conjugate addition to vinyl sulfones......Page 188
alpha-Alkylation of sulfoximines......Page 190
Alkylation of S-allylthiocarbamates......Page 191
Alkylation of allyl sulfones......Page 192
Nitrogen-stabilized Carbanions......Page 193
Lithiation by Li-Sn(IV) exchange......Page 194
Dipole-stabilized anions......Page 195
alpha-Alkylation of 1-aminosubstituted allyllithiums......Page 196
Metallation through hydrogen abstraction by lithiated bases......Page 197
Alkylation of phospholane oxides in the alpha-position......Page 200
Alkylation of allylphosphonates......Page 201
alpha-Alkylation of alkyl silanes......Page 202
Synthesis via allylzincation reaction......Page 203
C- versus O-Alkylation of beta-Dicarbonyls and Related Compounds......Page 204
Alkylation of Oxazoline, O-Stabilized Carbanions......Page 205
Alkylation of Enolate, S-Stabilized Carbanions......Page 206
Alkylation of Enolate, N-Stabilized Carbanions......Page 207
Alkylation of S,S- or Se,Se-Stabilized Carbanions......Page 209
Alkylation of N,S-Stabilized Carbanions......Page 210
Acknowledgements......Page 211
References......Page 212
Biographical sketch......Page 218
Radical Reactions......Page 220
Intramolecular reactions......Page 221
Displacement of Alcohol Derivatives......Page 222
Alkyl alcohol derivatives......Page 223
Allylic alcohol derivatives......Page 224
Propargylic alcohol derivatives......Page 227
Benzylic alcohol derivatives......Page 228
Vinyl alcohol derivatives......Page 229
Aryl alcohol derivatives......Page 232
Simple and vinylogous epoxides......Page 234
Cyclopropanation of Carbonyl and Carboxyl Compounds......Page 236
Radical Reactions......Page 237
Sulfides as leaving groups......Page 241
Sulfones and sulfonates as leaving groups......Page 242
Reactions with Tellurium Compounds......Page 243
References......Page 245
Biographical sketch......Page 249
1.06 One or More CC Bond(s) Formed by Substitution: Substitution of Carbon-Nitrogen, -Phosphorus, -Arsenic, -Antimony, -Boron, -Silicon, -Germanium, and -Metal Functions......Page 250
Quaternary Ammonium Salts......Page 251
Tertiary Amines......Page 253
Functionalized Benzotriazoles......Page 256
Azides......Page 260
Ring Opening of Aziridines......Page 261
Radical-mediated Processes......Page 265
The Stevens rearrangement......Page 266
Rearrangements of aziridines......Page 270
Substitution of Phosphorus Functions......Page 271
Substitution of Arsenic Functions......Page 272
Substitution of Antimony Functions......Page 274
Conjugate addition to alpha,beta-unsaturated ketones and aldehydes......Page 275
Conjugate addition to vinyl- and alkynylepoxides......Page 276
Aromatic and alkenic substitution......Page 277
With organoboron reagents......Page 278
With boronic acids and boronic esters......Page 279
Aliphatic substitution......Page 281
Alkylation......Page 282
Hydroxylation/aldol reactions......Page 285
Azomethine ylides......Page 287
Thiocarbonyl ylides......Page 291
Trimethylenemethane......Page 293
Substitution of Germanium Functions......Page 296
Substitution of Metal Functions......Page 297
References......Page 299
Biographical sketch......Page 304
Introduction......Page 306
Addition of Alkanes and Alkyl Electrophiles to Alkenes......Page 307
Hydroformylation......Page 308
Hydrocarboxylation......Page 309
Introduction and general aspects......Page 310
Addition of 1,3-dicarbonyl compounds and related nucleophiles......Page 311
Addition of other carbonyl compounds......Page 315
Addition of nitro compounds and other alpha-aminocarbanion equivalents......Page 317
Addition of silyl enol ethers and silylketene acetals: Mukaiyama-Michael reaction......Page 318
Addition of cyanide......Page 319
Alkyl addition......Page 320
Aryl and alkenyl addition......Page 322
Alkynyl addition......Page 324
Addition of stabilized nucleophiles......Page 325
References......Page 326
Biographical sketch......Page 330
1.08 One or More CC Bond(s) Formed by Addition: Addition of Carbon Radicals and Electrocyclic Additions to CC Multiple Bonds......Page 332
Stability and structure of alkyl and vinyl radicals......Page 333
Cyclic radical additions......Page 334
Acyclic radical additions......Page 335
Tin hydrides......Page 339
Silicon hydrides......Page 340
Carbon hydrides......Page 341
The Barton method and xanthates in radical reactions......Page 342
The borane method......Page 343
The atom transfer method......Page 344
Phosphorus hydrides......Page 345
Organotellurium compounds......Page 346
Electron-transfer processes......Page 347
Introduction......Page 348
Formation of other ring sizes......Page 349
Tin hydrides and germanium hydrides......Page 351
Hydrogen atom transfer reactions......Page 353
Carbon hydrides......Page 354
Atom transfer reactions......Page 355
Indium hydrides and gallium hydrides......Page 356
Samarium-mediated cyclization reactions......Page 357
Other metal-mediated radical cyclization reactions......Page 358
Intramolecular/intramolecular sequences......Page 359
Intermolecular/intramolecular additions......Page 360
Introduction......Page 361
Addition of metal carbenoids......Page 362
Thermal [2+2]-additions......Page 366
Photochemical [2+2]-additions......Page 367
Metal-catalyzed [2+2]-additions......Page 368
2-Alkylidenecyclopentane-1,3-diyls......Page 369
Trimethylenemethane acetals......Page 371
Transition metal-trimethylenemethane complexes......Page 372
Additions of allyl anions......Page 374
Meta-photocyclization of arenes......Page 375
Additions of carbonyl ylides......Page 376
Additions of thiocarbonyl ylides......Page 377
Additions of azomethine ylides......Page 379
Additions of azaallyl anions......Page 382
References......Page 384
Biographical sketch......Page 392
Types of Reaction......Page 394
Fritsch-Buttenberg-Wiechell rearrangement......Page 395
Wagner-Meerwein rearrangement......Page 396
Pinacol rearrangement......Page 401
Rearrangement of epoxides......Page 404
Semipinacol rearrangement......Page 407
Favorskii rearrangement......Page 410
Wolff rearrangement......Page 412
Westphalen-Lettré rearrangement of steroids......Page 414
[1,2]-Wittig rearrangement......Page 415
Rearrangement of ammonium ylides......Page 418
Rearrangement of oxonium ylides......Page 419
[1,3]-Sigmatropic rearrangements......Page 420
[2,3]-Wittig......Page 421
G as an alkyl group......Page 422
G as an allyl group......Page 423
G as a phosphorus-containing anion-stabilizing group......Page 424
G as an acid, ester, or amide......Page 425
Rearrangement of dienolates......Page 426
[2,3]-aza-Wittig rearrangement......Page 427
[2,3]-Wittig-Still rearrangement......Page 428
Rearrangement of ammonium ylides......Page 429
Rearrangement of oxonium ylides......Page 431
Rearrangement of sulfonium and selenonium ylides......Page 432
Claisen rearrangement......Page 433
Nazarov cyclization......Page 434
References......Page 436
Biographical sketch......Page 445
1.10 One or More =CH Bond(s) Formed by Substitution or Addition......Page 446
Reduction of aryl fluorides......Page 447
Reduction of aryl chlorides......Page 448
Reduction of aryl bromides......Page 449
Reduction of aryl iodides......Page 450
Reduction of vinyl fluorides......Page 451
Reduction of vinyl chlorides......Page 452
Reduction of vinyl bromides......Page 453
Reduction of vinyl iodides......Page 454
Reduction of phenols and derivatives......Page 455
Reduction of enol ethers and derivatives......Page 456
Reduction of aryl selenides and aryl tellurides......Page 457
Reduction of vinyl sulfides, sulfoxides, and sulfones......Page 458
Reduction of vinyl selenides......Page 459
Reduction of arylcarbon-nitrogen bonds......Page 460
Reduction of arylcarbon-phosphorus bonds......Page 462
Reduction of vinylcarbon-phosphorus bonds......Page 463
Reduction of aryl silanes......Page 464
Reduction of aryl germanes......Page 465
Reduction of vinyl silanes......Page 466
Reduction of arylcarbon-carbon bonds......Page 468
Reduction of vinylcarbon-carbon bonds......Page 469
Reduction of vinylcarbon-metal bonds......Page 470
Formation of (Z)-alkenes......Page 472
Addition of hydrogen to allenes......Page 474
References......Page 475
Biographical sketch......Page 481
1.11 One or More =C-C Bond(s) Formed by Substitution or Addition......Page 482
Friedel-Crafts alkylation......Page 483
Substitution by organometallic sp2 carbanions......Page 484
Alkyl nucleophiles......Page 486
Alkenyl nucleophiles......Page 487
Aryl nucleophiles......Page 488
Addition-elimination displacements of vinyl halides......Page 489
Alkyl nucleophiles......Page 490
Aryl nucleophiles......Page 491
Other methods......Page 492
Friedel-Crafts alkylation and related processes......Page 495
Substitution by organometallic sp2 carbanions......Page 497
Substitution of alkenyl oxygen leaving groups......Page 498
Substitution of aryl oxygen leaving groups......Page 499
Substitution of alkyl chalcogen leaving groups......Page 501
Substitution of alkenyl and aryl chalcogen leaving groups......Page 502
Substitution of Nitrogen......Page 503
General remarks on boron substitution reactions......Page 504
Substitution of arylboranes......Page 505
Substitution of alkenylboranes......Page 508
Substitution of alkylboranes......Page 509
Substitution of silicon and germanium......Page 510
Substitution of tin......Page 513
Substitution of a Metal......Page 516
Friedel-Crafts alkylations using alkenes and alkanes......Page 517
Transition metal-mediated substitution of arenes using alkenes......Page 518
Initiation by C-X bond insertion......Page 519
Initiation by C-H bond insertion......Page 522
Miscellaneous methods......Page 524
Nucleophilic Addition to Allenes......Page 525
General observations......Page 529
[4+2]-Cycloadditions......Page 530
Carbene Addition to Allenes......Page 533
References......Page 534
Biographical sketch......Page 550
1.12 One or More C=C Bond(s) Formed by Addition......Page 552
Catalysts......Page 553
Homogeneous Catalytic Hydrogenation......Page 555
Dissolving Metal Reductions......Page 556
Aluminum reagents......Page 558
Miscellaneous Reducing Agents......Page 560
[2+2]-Cycloaddition Reactions......Page 561
Diels-Alder Reactions......Page 564
1,3-Dipolar Cycloaddition Reactions......Page 568
Ene Reactions......Page 570
The Pauson-Khand Reaction......Page 572
Cyclotrimerization of Alkynes......Page 574
Hydroboration followed by C-C bond formation......Page 575
Hydroalumination followed by C-C bond formation......Page 576
Hydrostannylation followed by C-C bond formation......Page 577
Hydrozirconation followed by C-C bond formation......Page 578
Ionic Additions of Stabilized Carbanions to Activated Alkynes......Page 579
Additions of organolithium and Grignard reagents to alkynes......Page 580
Addition of organocopper reagents to activated alkynes......Page 581
Additions of organocuprate reagents to unactivated alkynes......Page 582
Addition of organoaluminum reagents to alkynes......Page 583
Other carbometallation reactions of alkynes......Page 585
Palladium-catalyzed Additions to Alkynes......Page 586
Intramolecular Free Radical Additions......Page 588
Addition of Simple Carbenes and Carbenoids to Alkynes......Page 590
Reaction of Fischer Carbene Complexes with Alkynes: The Dötz Synthesis of Phenols......Page 591
References......Page 592
Biographical sketch......Page 599
1.13 One or More C=C Bond(s) by Elimination of Hydrogen, Carbon, Halogen, or Oxygen Functions......Page 600
Dehydrogenation of Ketones and Aldehydes......Page 601
Dehydrogenation of Silyl Enol Ethers......Page 602
Decarboxylation......Page 603
Decarboxylation/dehydration......Page 604
Elimination of Dihalides......Page 605
Dehydrobromination......Page 607
Dehydroiodination......Page 608
Using Burgess’ reagent......Page 609
Dehydration by other methods......Page 610
Elimination of Alcohols (H-OR)......Page 611
Eliminative Ring Opening of Epoxides......Page 612
Elimination of a Sulfonic Acid......Page 613
Elimination of 1,2-Diols and Derivatives......Page 614
Deoxygenation of Epoxides and Halohydrins......Page 615
References......Page 616
Biographical sketch......Page 619
1.14 One or More C=C Bond(s) by Elimination of S, Se, Te, N, P, As, Sb, Bi, Si, Ge, B, or Metal Functions......Page 620
Elimination of sulfide, thiocyanate, and xanthate groups......Page 621
Elimination of selenide groups......Page 625
Elimination of sulfoxide groups......Page 626
Oxidative elimination from polymer-supported selenide derivatives......Page 631
Elimination of sulfones......Page 633
Julia olefination......Page 635
The Ramberg-Bäcklund reaction......Page 637
Elimination of Sulfonium, Selenonium, and Telluronium Salts and Ylides......Page 639
Elimination of Amine Oxides-The Cope Reaction......Page 641
Elimination of Quaternary Ammonium Salts-The Hoffmann Elimination......Page 642
Alkenes from Arenesulfonyl Hydrazones......Page 644
Elimination of Amine Derivatives......Page 649
Elimination of Nitro Groups......Page 650
Elimination of beta-hydroxyphosphane oxides and beta-hydroxyphosphonates: the Horner-Wittig reaction......Page 651
Via oxirane-opening reactions......Page 656
Elimination of Silicon Groups......Page 657
Elimination of beta-hydroxysilanes and delta-hydroxyallylsilanes......Page 658
Elimination of beta-sulfonyloxy-, beta-acyloxy-, and beta-alkoxysilanes, and delta-sulfonyloxy-, delta-acyloxy-, and delta-alkoxyallylsilanes......Page 659
Long-range elimination of hydroxy-, sulfonyloxy-, acyloxy-, and alkoxyallylsilanes......Page 664
Elimination of beta-halosilanes......Page 665
Elimination of beta-aminosilanes......Page 667
Elimination of sulfur-containing leaving groups......Page 668
Other eliminations of silanes......Page 669
Elimination of Germanium Groups......Page 671
Elimination of beta-substituted alkylboranes......Page 672
Elimination of beta-hydroxystannanes, derived ethers and esters......Page 673
Other eliminations of stannanes......Page 674
Elimination of Mercury......Page 677
Elimination of Transition Metals......Page 678
References......Page 680
Biographical sketch......Page 686
1.15 One or More C=C Bond(s) Formed by Condensation: Condensation of Nonheteroatom-linked Functions, Halides, Chalcogen, or Nitrogen Functions......Page 688
Catalysts......Page 689
Ring-closing metathesis......Page 691
Cross-metathesis......Page 696
ROM and tandem reactions......Page 698
Ene-yne metathesis......Page 700
Non-Chauvin metathesis......Page 705
Chromium-mediated Condensation......Page 707
Zinc-mediated Condensation......Page 709
Condensations Mediated by Other Metals......Page 710
Synthesis of beta-Lactones and Subsequent Decarboxylation......Page 713
McMurry Coupling of Carbonyl Compounds......Page 714
Alkylation of Sulfur(II)-stabilized Carbanions and Elimination......Page 715
The Julia reaction and related transformations......Page 716
The Ramberg-Bäcklund reaction......Page 724
Alkylation of Selenium(II)- and Selenium(IV)-stabilized Carbanions Followed by Elimination......Page 728
Reactions of Diazo Compounds......Page 729
The Mannich Reaction......Page 731
The Aza Wittig Reaction......Page 732
References......Page 733
Biographical sketch......Page 741
1.16 One or More C=C Bond(s) Formed by Condensation: Condensation of P, As, Sb, Bi, Si, Ge, B, or Metal Functions......Page 742
Alkenation via the Wittig Reaction......Page 743
Mechanism......Page 744
Stabilized ylides......Page 745
Formation of (E)-alkenes via Wittig-Schlosser modification......Page 746
Benzylic ylides......Page 747
Asymmetric Wittig reaction......Page 748
Comparison of stabilized, nonstabilized, and semistabilized ylides......Page 749
Mechanism......Page 750
Bismuthonium Ylides......Page 751
Phosphonate-stabilized carbanions (Horner-Wadsworth-Emmons reaction)......Page 752
Formation of (E)-alkenes......Page 753
Formation of (Z)-alkenes......Page 755
Phosphoryl-stabilized carbanions (Horner reaction)......Page 757
Stereoselective formation of (E)- and (Z)-alkenes......Page 758
Asymmetric Horner-Wadsworth-Emmons and Horner reactions......Page 761
Mechanism......Page 762
Methylenation reactions......Page 763
Formation of aliphatic alkenes......Page 764
Formation of functionalized alkenes......Page 765
Boron-mediated Alkenation......Page 766
Tebbe Reagent......Page 767
Petasis Reagents......Page 768
Takeda Reagents......Page 769
Takai-Lombardo Reagents......Page 770
References......Page 771
Biographical sketch......Page 777
Introduction......Page 780
Cleavage of One C-H (or One X-H, XequalHeteroatom) and One C-C (or One Heteroatomic) Bond......Page 781
Pyrolysis of acetates and related esters......Page 782
Pyrolysis of xanthate esters......Page 784
Other concerted pyrolytic eliminations......Page 787
Cleavage of One C-H and One C-S Bond, Including Pyrolysis of Sulfoxides......Page 788
Cleavage of One C-H and One C-Se Bond: Pyrolysis of Selenoxides......Page 791
Retro-[2+2]-cycloadditions......Page 796
Retro-[4+2]-cycloadditions (Retro-Diels-Alder Reactions)......Page 797
Formation of Dienes and Polyenes......Page 800
Retro-cycloaddition Reactions......Page 801
Retro-cheletropic Reactions......Page 806
References......Page 810
Biographical sketch......Page 814
1.18 One or More =CH, =CC, and/or C=C Bond(s) Formed by Rearrangement......Page 816
Sigmatropic migrations of hydrogen......Page 817
Acid- and base-catalyzed migrations of a hydrogen atom......Page 822
Metal-catalyzed migrations of hydrogen......Page 824
Sigmatropic migrations of C-C bonds......Page 826
Photochemical rearrangement of vinylcyclopropanes......Page 828
Acid or metal-catalyzed rearrangement of vinylcyclopropanes......Page 829
Rearrangement of vinylcyclobutanes......Page 830
Thermal/photochemical Cope rearrangement......Page 832
Catalysis of the Cope rearrangement......Page 834
Aza-Cope rearrangement......Page 835
Anionic oxy-Cope rearrangements......Page 836
Anionic amino-Cope rearrangements......Page 839
Cope rearrangement of divinyl cycloalkanes......Page 840
Claisen rearrangement (Y=C-C-O)......Page 844
Claisen rearrangement of allyl/propargyl vinyl ethers......Page 845
Aromatic Claisen rearrangement......Page 849
The Eschenmoser amide acetal and Johnson orthoester Claisen rearrangements......Page 853
The Ireland ester enolate Claisen rearrangement......Page 855
The Carroll rearrangement......Page 858
The Holmes-Claisen rearrangement......Page 859
The Kazmaier-Claisen rearrangement......Page 860
Thia-Claisen rearrangement......Page 861
Where Z=N; the aza-Claisen rearrangement and related processes......Page 862
Other Heteroatom Variants......Page 866
Where Z and Z’=chalcogen......Page 867
Where Z and/or Z’=nitrogen......Page 869
Where Y=Z......Page 870
Where Z, Z’=chalcogen......Page 871
Where Z and/or Z’=nitrogen, phosphorus......Page 872
Tandem and Higher Sigmatropic Rearrangements......Page 875
Ring opening of cyclopropanes......Page 877
Photochemical ring opening of cyclic ketones......Page 879
Rearrangement of epoxides......Page 880
References......Page 883
Biographical sketch......Page 907
1.19 Tricoordinate Carbanions, Cations, and Radicals......Page 908
General Aspects......Page 909
Directed Deprotonation......Page 910
Diastereo- and enantioselective deprotonation......Page 911
Chiral enolates......Page 912
Oxidative Addition......Page 913
Direct reduction of organohalides......Page 914
Reduction of organohalides mediated by arenes......Page 915
Organohalide-organometallic equilibria......Page 916
General Aspects......Page 918
1,4-Additions (Michael-type reactions)......Page 919
Carbometallation......Page 920
Hydrometallation......Page 922
General Aspects of Transmetallation: Tuning the Reactivity......Page 923
Titanium dicarbanions (the Kulinkovich reaction)......Page 924
Zirconium dicarbanions and the Dzhemilev reaction......Page 925
General Literature Survey......Page 927
Historical Background......Page 928
Carbenium and Carbonium Ion Nomenclature......Page 930
Methods for Generating and Investigating Ions in the Gas Phase......Page 931
Gas-phase Thermochemical Data......Page 932
Examples of Carbenium Ions in the Gas Phase......Page 936
Aromatic Carbeniun Ions......Page 939
TheCyclopropyl Substituent Effect......Page 940
The Effect of the Nature of the Nucleofugal Group......Page 941
The Use of Super-Acids......Page 943
Carboranes as Super-Acids......Page 944
Intermolecular Hydride Transfer Reactions......Page 945
Carbocations Generated upon Irradiation......Page 946
Carbocations by Fragmentation of Alkoxy(chloro)carbenes......Page 948
Hydrocarbon Alkylation and Cracking with Zeolites......Page 949
As Intermediates in Heterolysis......Page 950
Heterolyses of Substrates alpha-Substituted by Electron-withdrawing Groups......Page 951
Remote Allyl Substituent Effects......Page 953
Anchimeric Assistance versus sigma(C,C) Hyperconjugation......Page 954
Anchimeric Assistance by Heteroelements......Page 957
Hyperconjugation and Participation by Metals......Page 958
Characterization of Cationic Electrophiles and Their Reactivity with Nucleophiles......Page 961
Carbocation Rearrangements......Page 963
Carbodi- and Polycations......Page 968
Carboctions in Living Systems......Page 969
Mechanism of the Prenyl Transfer Reaction and Monoterpene Biosynthesis......Page 970
Biosynthesis of Sesquiterpenes, Diterpenes......Page 971
Squalene and Triterpenes......Page 972
Nonmetal Hydrogenase-catalyzed Hydrogenation......Page 975
Carbocations and Medicinal Chemistry......Page 976
General Features of Radical Formation......Page 979
General literature survey......Page 980
Thermal radical production......Page 981
Electrochemical generation of radicals......Page 983
The reaction of dioxygen with organometallics......Page 985
Single-electron chemical reductions......Page 986
Single-electron chemical oxidations......Page 988
The radical-polar crossover reaction......Page 990
Rate constants for abstractions......Page 992
Intermolecular addition reactions of radicals......Page 993
Enhancement of alkene electron affinity by coordination with a Lewis acid......Page 997
Abstraction of hydrogen from aldehydes: the hydroacylation of alkenes......Page 999
Intermolecular radical additions to hetero double bonds......Page 1000
Five-membered versus six-membered ring formation......Page 1007
4-exo and 5-endo cyclizations......Page 1010
n-exo and endo cyclizations......Page 1011
3-exo-Cyclization: Homoallyl/cyclopropylmethyl Isomerization......Page 1012
Ring contractions......Page 1014
Cascade radical cyclizations......Page 1015
Radical fragmentation......Page 1018
Living radical polymerization......Page 1021
Metal-catalyzed living radical polymerization......Page 1022
References......Page 1023
Biographical sketch......Page 1036
1.20 Allenes and Cumulenes......Page 1038
Isomerization of alkynes and diynes......Page 1039
Isomerization of enynes......Page 1040
Propargylic rearrangement......Page 1041
Dehalogenation of alkynic halides......Page 1042
Reduction of polyunsaturated hydrocarbons......Page 1043
Reduction of propargylic derivatives......Page 1044
Palladium-catalyzed reduction of propargylic derivatives......Page 1045
Elimination involving H-migration......Page 1046
Hydrolysis of alkynic silanes......Page 1047
Alkylcuprates as nucleophiles......Page 1048
Stoichiometric organocopper reagents as nucleophiles......Page 1050
Copper(I)-catalyzed nucleophilic substitution......Page 1052
Organocopper-mediated ring-opening reactions......Page 1053
Copper-mediated 1,n-addition reactions......Page 1054
Nucleophilic Substitution with Organomagnesium Reagents......Page 1055
Miscellaneous Nucleophilic Substitutions......Page 1056
Lithium derivatives......Page 1057
Magnesium, aluminum, and manganese derivatives......Page 1058
Tin-mediated allenylation reactions......Page 1059
Reactivity of propargyl silanes......Page 1060
Boron chemistry for allene synthesis......Page 1062
Allene synthesis via titanium derivatives......Page 1063
Indium-mediated allene synthesis......Page 1064
Palladium-mediated Coupling Reactions......Page 1065
[2,3]-Wittig rearrangement......Page 1069
[3,3]-Claisen-Cope rearrangement......Page 1070
Miscellaneous......Page 1072
Desulfurization, decarboxylation, and related reactions......Page 1073
Elimination of HX......Page 1074
Elimination of XY......Page 1076
Reaction of a ketene and an alkylidene phosphorane......Page 1080
Reaction of a ketone and a vinylidene phosphorane......Page 1082
Addition of carbene moieties to double bonds......Page 1083
Dehalogenation of halocyclopropanes......Page 1084
Reactions Involving Coordinated Organometallic Species......Page 1085
Intramolecular Rearrangement with Formation of Heteroatom-Carbon Bond......Page 1086
Photorearrangement of vinylidenecyclopropanes......Page 1088
Miscellaneous Reactions......Page 1089
References......Page 1090
Biographical sketch......Page 1100
Introduction......Page 1102
Reduction of Alkynyl-metalloid Functions......Page 1103
Alkynes by C-C Bond Formation......Page 1104
The reaction of alkynyl carbanions with alkyl halides......Page 1105
Reaction of terminal alkynes with aryl, alkenyl, and allenyl halides/triflates in the presence of catalytic palladium(II) or palladium(0) compounds in the absence of a copper co-catalyst......Page 1110
Reaction of terminal alkynes with aryl, alkenyl, and allenyl halides in the presence of a copper co-catalyst......Page 1113
Reaction of terminal alkynes with aryl, alkenyl, and allenyl halides/triflates in the presence of catalytic palladium(II) or palladium(0) compounds, a copper co-catalyst and a base......Page 1115
Reaction of terminal metallated alkynes with aryl, alkenyl, and allenyl halides in the presence of catalytic palladium(II) or palladium(0) compounds and a base......Page 1127
Substitution reactions of alkynyl halides......Page 1130
Substitution of alkyl-oxygen functions......Page 1134
The reaction of metallated alkenyl sulfonates in the presence of catalytic quantities of Pd(II) or Pd(0) compounds......Page 1139
The reaction of terminal alkynes with alkenyl and sulfonates in the presence of catalytic quantities of Pd(II) or Pd(0) compounds and a base......Page 1140
Substitution of sulfur, selenium, or tellurium functions......Page 1141
Substitution of nitrogen, phosphorus, arsenic, antimony, or bismuth functions......Page 1143
Oxidative homocoupling reactions of terminal alkynes and their derivatives......Page 1144
Addition to carbon-carbon multiple-bonded functions......Page 1146
1,2-Addition to carbon-oxygen double-bonded functions......Page 1147
1,2-Addition to carbon-chalcogen double-bonded functions......Page 1153
1,2-Addition to carbon-nitrogen multiple-bonded functions......Page 1154
1,2-Addition-elimination reactions......Page 1157
1,4-Addition reactions......Page 1160
Substitution of halogen......Page 1162
Substitution of oxygen functions......Page 1164
1,2-Addition to carbon-oxygen double-bonded functions......Page 1165
1,2-Additions to carbon-nitrogen multiple-bonded functions......Page 1170
1,4-Addition reactions......Page 1171
Elimination of carbon functions......Page 1172
Dehydrohalogenation......Page 1173
Elimination of oxygen functions......Page 1177
Elimination of sulfur, selenium, or tellurium functions......Page 1179
Elimination of nitrogen functions......Page 1180
Elimination of boron, silicon, or germanium functions......Page 1183
Formation by isomerization reactions......Page 1184
References......Page 1185
Ions, Radicals, Carbenes, and Other Monocoordinated Systems......Page 1196
General Introduction......Page 1197
Formation of vinylic carbanions by deprotonation, metal-halogen exchange, and transmetallation......Page 1198
Applications in synthesis......Page 1199
Formation of vinylic carbanions by deprotonation, metal-halogen exchange, and transmetallation......Page 1201
Formation of vinylic carbanions by deprotonation, metal-halogen exchange, and transmetallation......Page 1202
Applications in synthesis......Page 1203
Applications in synthesis......Page 1206
Formation by metal-halogen exchange......Page 1207
Vinylphosphorus Reagents......Page 1208
Formation by addition to alkynes and allenes......Page 1209
Vinylsilicon Reagents......Page 1214
Formation of vinylic carbanions by deprotonation, metal-halogen exchange, and transmetallation......Page 1215
Formation by addition to alkynes and allenes......Page 1216
Applications in synthesis......Page 1217
Applications in synthesis......Page 1218
Formation by addition to alkynes and allenes......Page 1220
Applications in synthesis......Page 1228
Vinyltitanium Reagents......Page 1233
Formation by addition to alkynes and allenes......Page 1234
Formation by addition to alkynes and allenes......Page 1236
Formation by addition to alkynes and allenes......Page 1237
Preparation of vinyliodonium salts......Page 1238
Vinylic SN2 mechanism......Page 1239
Rearrangements......Page 1242
Primary vinylic cations in synthesis......Page 1243
Formation of Secondary and Tertiary Vinylic Cations from Iodonium Salts......Page 1244
Formation of Vinylic Cations by Bond Scission......Page 1245
Formation of Vinylic Cations by Addition to Alkynes and Alkenes......Page 1246
General Introduction......Page 1247
Bromides......Page 1248
Iodides......Page 1250
Selenium......Page 1253
Formation of Vinylic Radicals by Addition to Alkynes and Allenes......Page 1254
Monocoordinate Carbocations and radicals......Page 1261
General Introduction......Page 1262
Alkynyllithium Reagents......Page 1263
Alkynylmercury Reagents......Page 1264
Alkynylruthenium Reagents......Page 1265
Alkynyltin Reagents......Page 1266
General Introduction......Page 1268
Formation of Primary Vinylidene Carbenes from Iodonium Salts......Page 1269
Formation of Vinylidene Carbenes via Other Routes......Page 1270
References......Page 1271
Biographical sketch......Page 1278