Applications I. Main Group Compounds in Organic Synthesis

Comprehensive Organometallic Chemistry III.pdf......Page 1
Lithium......Page 2
Superbases and their Constitution......Page 3
Metallation of Alkenes in the Vinylic Position......Page 4
Metallation of Alkenes, Dienes, and Polyenes at the Allylic Position......Page 6
Trapping of Allylpotassium Reagents with Carbon Electrophiles......Page 10
Stereoselective Preparation of Allylmetallic Reagents......Page 12
Reaction of Heterosubstituted Allylmetal Reagents with Electrophiles......Page 13
Metallation of Dienes and Polyenes......Page 14
Metallation of Arenes......Page 15
Metallation of Heterosubstituted Arenes......Page 17
Metallation of Hetarenes......Page 22
Metallation of Alkylarenes and Alkyl-hetarenes......Page 24
References......Page 27
Direct Oxidative Addition of Magnesium to Organic Halides......Page 31
Metallation Reactions with Magnesium Amides......Page 33
Hydromagnesiation of Olefins and Acetylenes......Page 34
The Halogen-Magnesium Exchange Reaction......Page 35
Scope and Classification......Page 43
Transition metal-catalyzed cross-coupling reactions of alkyl halides and sulfonates......Page 44
Ring opening of small cycles, acetals, and thioacetals......Page 45
Miscellaneous reactions......Page 46
Transition metal-catalyzed cross-coupling reactions......Page 47
Allylic substitution reactions......Page 52
Synthesis of carbonyl compounds using Grignard reagents......Page 54
Catalyzed addition to non-activated C=C bonds......Page 55
1,4-Addition to alpha,beta-unsaturated carbonyl compounds......Page 56
Addition to other activated alkenes......Page 59
Addition to triple carbon-carbon bonds......Page 61
Addition to carbon-oxygene double bonds......Page 63
Addition to the carbon-nitrogen multiple bonds......Page 64
Electrophilic amination and reactions with nitroarenes......Page 70
Synthesis of cyclopropanes......Page 71
Various Reactions of Grignard Reagents......Page 72
References......Page 73
The direct insertion of zinc metal......Page 80
The halide-zinc exchange reaction......Page 84
Lithium-zinc exchange......Page 86
Boron-zinc exchange......Page 88
Zirconium-zinc exchange......Page 92
Preparation of allylic zinc compounds by fragmentation......Page 93
Preparation of dialkylzinc compounds by hydrozincation of alkenes......Page 94
Substitution reactions......Page 95
Asymmetric substitution reactions......Page 98
Addition reactions......Page 102
Asymmetric addition reactions......Page 108
Negishi cross-coupling......Page 116
Barbier reaction......Page 122
Cyclopropanations......Page 123
Methylene homologation and related reactions......Page 126
Preparation and Reaction of Zincates......Page 130
Preparation and Reactivity of Bimetallic Reagents of Zinc......Page 131
Cadmium Reagents in Organic Synthesis......Page 132
References......Page 133
Boron......Page 143
Transmetallation between organometallic compounds and BX3......Page 144
Uncatalyzed hydroboration of alkenes and alkynes......Page 147
Hydroboration of alkenes and alkynes......Page 151
Asymmetric hydroboration......Page 153
Non-metal catalysts......Page 155
Haloboration of terminal alkynes......Page 156
Diboration of alkenes and alkynes......Page 157
Silylboration of alkenes and alkynes......Page 161
Stannylboration of alkenes and alkynes......Page 162
Germylboration......Page 163
Catalyzed borylation of organic halides......Page 164
Cross-coupling reactions of diborons......Page 165
Cross-coupling reaction of pinacolborane......Page 168
Catalyzed borylation of aliphatic and aromatic C-H bonds......Page 169
Aromatic C-H borylation......Page 170
Benzylic C-H borylation......Page 172
Homologation of B-C bond via insertion of nucleophiles possessing a leaving group......Page 173
[2+4]-cycloaddition (Diels-Alder reaction)......Page 176
Metal-catalyzed cycloaddition......Page 178
Cyclopropanation......Page 179
Addition of metallic reagents......Page 180
Metal-catalyzed reactions of alkenyl- and alkynylboron compounds......Page 181
Addition and coupling reactions of boron-substituted carbanions......Page 182
Other methods for functionalization of remote sites......Page 183
Protodeboronation......Page 184
Oxidation......Page 185
Halogenolysis......Page 186
Other transformations......Page 187
Boron-Mannich reactions......Page 188
Nucleophilic alkylation of C=O, C=N, and enones......Page 190
Synthesis and reactions of allylboron compounds......Page 192
Asymmetric allylboration......Page 195
Aldol Reaction of Boron Enolates......Page 198
Radical Addition and Coupling Reactions......Page 200
Transmetallation to other Metals for Addition and Coupling Reactions......Page 202
Reactions of B-alkylboron compounds......Page 204
Reactions of B-arylboron compounds......Page 206
Reactions of B-allyl- and alkynylboron compounds......Page 210
Reactions leading to ketones (acylation reactions)......Page 211
Conjugate addition to electron-deficient alkenes......Page 212
Addition to alkenes and alkynes......Page 213
Addition to C=O and C=N bonds......Page 215
Copper-mediated C-N bond formation......Page 216
Copper-mediated C-O bond formation......Page 217
Copper-mediated C-S bond formation......Page 218
Boron as Lewis Acid Catalysts......Page 219
Boranes as Reducing Reagents......Page 222
References......Page 226
Aluminum......Page 243
Introduction......Page 244
Aluminum(iii)-carbon interactions......Page 245
Al(0)- or Al(i)-carbon interactions......Page 248
Aluminum-Halogen Covalent and Non-covalent Bonds......Page 249
Aluminum(iii)-Oxygen Covalent and Non-covalent Bonds......Page 250
Aluminum(iii)-Nitrogen Covalent and Non-covalent Bonds......Page 253
Aluminum(iii)-Sulfur-Selenium and -Tellurium Covalent and Non-covalent Bonds......Page 255
Mixed Covalent and Non-covalent Bonding Systems Involving Aluminum(iii)-Oxygen, -Nitrogen, and -Sulfur Bonds......Page 256
Aluminum(iii)-Phosphine Covalent and Non-covalent Bonds......Page 257
Bonds in Organoaluminum(ii) Compounds: Al-Al Bonds......Page 258
Bonds in Organoaluminum(i) Compounds: Al-Al Bonds......Page 259
Aluminum(i)-Boron Bonds......Page 261
Aluminum-Transition Metal Bonds......Page 262
Aluminum(iii)-tin exchange......Page 263
Aluminum(iii)-boron exchange......Page 264
Direct Alumination of Aromatic Rings......Page 265
Carboalumination and Hydroalumination......Page 266
New Aspects in Reactivity of Organoaluminum Compounds......Page 268
Aluminum alkyls in reaction with protic groups......Page 269
Aluminum alkyls in alkylation and deprotonation......Page 270
Aluminum alkyls in polymerization......Page 272
Aluminum alkyls in reactions with carbon-carbon multiple bonds, oxiranes, and other functional groups......Page 274
Organic Group-selective Transfer from Aluminum(iii) Ate Complexes to Electrophiles......Page 277
Ligand-induced Geometrical Diversity Affording New Reactivity of Organoaluminum(iii) Compounds......Page 279
Cationic Organoaluminum Compounds......Page 281
Low-coordinate cationic organoaluminum(iii) compounds (two to four coordinate)......Page 284
High-coordinate cationic organoaluminum(iii) compounds (five or six coordinate)......Page 286
References......Page 288
Silicon......Page 295
Electrophilic Substitution......Page 296
Reactions Forming Silylated Products......Page 297
Palladium-catalyzed reactions......Page 299
Rhodium-catalyzed reactions......Page 300
Copper-promoted reactions......Page 301
Lewis acid-promoted allylation......Page 302
New types of carbonyl allylation......Page 304
Asymmetric allylation of aldehydes, ketones, and acetals......Page 306
Allylation of Carbon-Nitrogen Double Bonds......Page 308
Tandem Carbon-Carbon Bond Formation......Page 310
Ene Reactions......Page 311
1,2-Silyl-migrative cycloaddition......Page 312
[2+2]-Cycloaddition......Page 314
Other cycloaddition without 1,2-silyl migration......Page 315
Allylation of Unactivated Alkynes and Alkenes......Page 316
Acylsilanes......Page 317
Cyanosilanes......Page 320
Other Functionalized Organosilanes......Page 321
Silacyclopropanes......Page 322
Cyclopropylmethylsilanes......Page 324
Alkylation......Page 325
Alkenylation and Alkynylation......Page 326
Arylation......Page 328
References......Page 329
Tin......Page 338
Bu3SnH-promoted Radical Reactions......Page 339
Radical Cyclizations......Page 340
Intermolecular Radical Coupling......Page 341
Tin Hydrides as Catalytic Use......Page 342
Fluorous Tin Hydrides......Page 343
Polymer-supported Tin Hydrides......Page 344
Halogenotin Hydrides......Page 345
Hydrostannation to Alkynes......Page 347
General......Page 348
Equimolar Lewis Acid-promoted Reactions......Page 349
Lewis Acid-catalyzed Reactions......Page 351
Asymmetric Reactions......Page 352
Barbier-type Reactions......Page 354
Lewis Acid-promoted Reactions......Page 355
Catalytic Asymmetric Reactions......Page 356
General......Page 357
Aldol and Its Related Reactions......Page 358
Highly Coordinated Tin Enolates......Page 359
Tin Enolate Generation from Enone with Bu3SnH......Page 360
Micellaneous Generation of Tin Enolates......Page 361
Tin(ii) Enolates......Page 362
Coupling with Halides......Page 363
Tin Alkoxides......Page 364
Tin Sulfides......Page 365
Tin Amides......Page 366
Tin Halides......Page 367
Stannyllithiums......Page 368
Stannylsilanes......Page 369
Stannylcuprates......Page 370
References......Page 372
Introduction......Page 377
Arylation of Dicarbonyl Compounds......Page 378
Mechanism and influence of the ligands and of the reaction conditions......Page 383
Diastereoselectivity studies......Page 385
Enantioselective arylation reactions......Page 387
Arylation of Ketone Derivatives......Page 388
Arylation of Phenols......Page 391
Arylation of Aniline and other Nitrogen Derivatives......Page 395
Alkenylation Reactions......Page 396
Alkynylation Reactions......Page 398
Copper-catalyzed Reactions......Page 401
Mechanism of the copper diacylate-catalyzed arylations......Page 407
Palladium Cross-coupling with Organolead Reagents......Page 408
Rhodium-catalyzed Reactions......Page 410
Alkyllead in Co-catalyzed Metathesis Reactions......Page 411
Miscellaneous Reactions of Organolead Compounds......Page 414
Reactions of Triaryllead Anions......Page 415
Trifluoromethylation Reaction......Page 416
References......Page 417
Introduction......Page 421
Barbier-type reactions......Page 422
Pd-catalyzed carbon-carbon bond-forming reactions......Page 423
Carbon-heteroatom bond-forming reactions......Page 424
Carbon-carbon bond-forming reactions using tetraorganylantimony(v) compounds......Page 425
Carbon-carbon bond-forming reactions using pentaarylantimonys......Page 426
Pd-catalyzed carbon-carbon bond-forming reactions......Page 427
Carbon-heteroatom bond-forming reactions......Page 428
Barbier-type and related reactions......Page 429
BiX3-catalyzed carbon-carbon bond-forming reactions......Page 431
Pd- and Rh-catalyzed carbon-carbon bond-forming reactions......Page 434
BiX3-mediated carbon-heteroatom bond-forming reactions......Page 436
Cu-mediated carbon-heteroatom bond-forming reactions......Page 438
Oxidations......Page 439
C-arylation of enolisable substrates......Page 440
Carbon-carbon bond-forming reactions using bismuthonium salts......Page 442
Carbon-carbon bond-forming reactions using bismuth ylides......Page 443
Pd-catalyzed carbon-carbon bond-forming reactions......Page 444
Carbon-heteroatom bond-forming reactions using bismuthonium salts......Page 445
Oxidations......Page 446
References......Page 448
Introduction and General Aspects......Page 453
Electrophilic Selenium......Page 455
Nucleophilic Selenium......Page 464
Selenium-stabilized Carbanions and Carbocations......Page 468
Radical Reactions Using Selenium Precursors......Page 472
Selenoxides......Page 475
Eliminations......Page 476
Rearrangements......Page 477
Trivalent derivatives......Page 479
Tetravalent derivatives......Page 480
Hexavalent derivatives......Page 481
Synthesis of selenocarbonyl compounds......Page 482
Reactions with selenocarbonyl compounds......Page 483
Selenium-containing compounds as ligands......Page 485
Selenium-containing compounds as catalysts......Page 486
References......Page 488
Introduction......Page 496
Copper reagents......Page 497
Substrate scope......Page 504
Stereoselectivity......Page 509
Substitution reactions......Page 512
Allylic substrates......Page 513
Propargylic substrates......Page 518
Carbocupration and related reactions......Page 522
Copper catalysts......Page 526
Enantioselectivity......Page 529
Substitution reactions......Page 543
Carbometallation and other reactions......Page 546
Allylation and Aldol Reactions......Page 547
Cycloisomerizations and Rearrangements......Page 553
Cycloadditions......Page 559
Other Reactions......Page 563
Gold......Page 564
C-H Bond Activation......Page 565
Activation of Alkynes......Page 566
Activation of Allenes......Page 568
References......Page 570
Tellurium......Page 581
Introduction......Page 582
Main Classes of Organic Tellurium Compounds......Page 583
From Elemental Tellurium and Organolithium and Grignard Reagents......Page 586
Reaction of aromatic substrates with tellurium tetrachloride......Page 587
Addition of tellurium tetrachloride to alkenes and alkynes......Page 588
Halogenolysis of diorganoditellurides......Page 589
Organotellurium Halides......Page 590
Aryltellurium Oxides and Aryltellurinic Acid Anhydrides......Page 591
Reduction of functional groups......Page 592
Epoxides and aziridines ring openings......Page 593
Heteroatoms removals......Page 594
Carbon-carbon bond formation mediated by tellurium compounds......Page 595
Interaction of Nucleophilic Tellurium with Organic Substrates with Incorporation of Tellurium......Page 596
Arylation reactions......Page 597
Hydrotelluration of alkynes......Page 598
Monosubstituted alkynes conjugated to a carbon-carbon double bond......Page 600
Alkynes bearing electron-stabilizing groups......Page 601
Hydrotelluration of alkenes......Page 602
Vinylic substitution......Page 604
Reaction with Organometallics......Page 607
Preparation of vinylic tellurides......Page 608
Reaction with Activated Aromatics, Alkenes, and Alkynes......Page 611
Free Radical Species......Page 612
Homolytic Cleavage of Tellurium-Tellurium or Tellurium-Silicon Bonds......Page 614
Homolytic Cleavage of sp3-Carbon-Tellurium Bonds......Page 615
Telluroxide Elimination......Page 616
Tellurium-Metal Exchange......Page 617
Tellurium-lithium exchange of alkyl, alkynyl, aryl, and aroyl tellurides......Page 619
Tellurium-lithium exchange of vinylic tellurides......Page 622
Tellurium-zinc exchange......Page 625
Tellurium-copper exchange......Page 627
Coupling Reactions......Page 628
Copper-mediated couplings......Page 630
Palladium-mediated couplings......Page 632
Free Radical Processes to Remove Tellurium from Organic Substrates......Page 634
Conclusion......Page 635
References......Page 638
Indium and Gallium......Page 643
Oxidative Addition to Organic Halides......Page 644
Allylation and Propargylation of Carbonyl Compounds......Page 645
Regioselective Carbonyl Allylation......Page 647
Introduction......Page 650
Oxygen-bearing allylindium reagents......Page 652
Effect of the substituent adjacent to the carbonyl group......Page 658
Enantioselective Allylation......Page 666
Allylation of quinones and dicarbonyl compounds......Page 669
Cyclization via intramolecular allylation......Page 673
Reactions of allylindium derived from allylic dihalo compounds......Page 675
Reactions with acid halides and related compounds......Page 677
Miscellaneous carbonyl allylation reactions......Page 678
Allylation of Imines, Enamines, and Nitriles......Page 681
Allylindation of Alkenes and Alkynes......Page 687
Reactions of Allylindium Prepared by Redox Transmetallation with Pd or Ni......Page 692
Other Reactions of Allylindium Reagents......Page 696
Reformatsky and Related Reactions......Page 699
Transition Metal-catalyzed Coupling Reactions......Page 702
Reduction of carbonyl compounds......Page 707
Dehalogenation and other reactions......Page 709
Carbon-Carbon Bond Formation via Radical Reactions......Page 711
Allylic alkylation......Page 713
Alkynylation......Page 714
Miscellaneous reactions......Page 716
Transmetallation......Page 717
Addition to carbonyl compounds......Page 718
Carbogallation......Page 723
Radical reactions......Page 729
Reduction......Page 732
Coupling reaction......Page 734
Use as Lewis acids and bases......Page 735
References......Page 739