Applications II. Transition Metal Compounds in Organic Synthesis 2

Comprehensive Organometallic Chemistry III.pdf......Page 1
Introduction......Page 3
Reactions with Organoboron Reagents: The Suzuki-Miyaura Reaction......Page 4
New coupling partners......Page 6
Palladacycle complexes as catalysts precursors......Page 8
Catalytic systems composed of Pd(0) or Pd(ii) derivatives and phosphines......Page 9
Catalytic systems composed of Pd(0) or Pd(ii) and N-heterocyclic carbenes......Page 10
Supported and heterogeneous systems......Page 12
Non-palladium-based systems......Page 13
Palladacycle complexes as catalysts precursors......Page 14
Catalytic systems composed of Pd(0) or Pd(ii) and phosphines......Page 15
Catalytic systems composed of Pd(0) or Pd(ii) and N-heterocyclic carbenes......Page 16
Reactions of Terminal Alkynes......Page 17
Palladacycle complexes and systems composed of Pd(0) or Pd(ii) derivatives and N-heterocyclic carbenes as catalysts precursors......Page 18
Alkynylsilicon reagents......Page 19
Alkynylzinc reagents......Page 20
The Cadiot-Chodkiewicz reaction......Page 21
Nickel-based systems......Page 22
Iron-based systems......Page 23
Palladium-based systems......Page 24
Reactions with Organosilicon Reagents: The Hiyama Reaction......Page 25
Coupling of alkenylsilanes......Page 26
Fluoride-free systems......Page 28
Arylzinc reagents......Page 29
Alkenyl- and alkylzinc reagents......Page 31
References......Page 32
Introduction......Page 40
Deoxygenative Coupling of Carbonyl Compounds to Olefins: McMurry Coupling......Page 41
Olefination of Carbonyl Compounds with Polyhaloalkanes and Low-Valent Metals......Page 42
Pinacol-Type Coupling Reactions......Page 43
Titanium-based reagent systems......Page 44
Diastereoselective coupling reactions of aromatic aldehydes......Page 45
Mechanism of pinacol coupling with low-valent titanium......Page 48
Asymmetric pinacol coupling reactions......Page 49
Intramolecular coupling to cyclic 1,2-diols and its synthetic applications......Page 52
Preparation of samarium(ii) reagents for pinacol coupling......Page 53
Catalytic use of samarium complexes for pinacol coupling......Page 54
Additives and solvents to accelerate pinacol coupling......Page 55
Samarium(iii) ketyl radical and mechanism......Page 56
Diastereoselectivity......Page 58
Intramolecular cyclization......Page 61
Vanadium-based reagent systems......Page 63
Chromium-based reagent systems......Page 64
Reductive Coupling of Imines......Page 65
Cross-Coupling Reactions between Carbonyl Compounds and Imine Derivatives......Page 67
References......Page 70
Introduction......Page 75
Alkylation of Acyclic and Symmetric Allylic Esters......Page 76
Alkylation of Acyclic Monosubstituted Allylic Esters......Page 90
Alkylation of Cyclic Allylic Esters......Page 91
Allylation of Prochiral Nucleophiles......Page 96
Asymmetric Allylic Alkylation of Allylic Alcohols and their Derivatives Catalyzed by Transition Metals other than Palladium......Page 98
Copper-catalyzed Alkylation......Page 99
Nickel-catalyzed Alkylation......Page 102
Platinum-catalyzed Alkylation......Page 103
Rhodium-catalyzed Alkylation......Page 104
Iridium-catalyzed Alkylation......Page 105
Ruthenium-catalyzed Alkylation......Page 108
Molybdenum-catalyzed Alkylation......Page 109
Tungsten-catalyzed Alkylation......Page 111
Other Reaction Systems in Asymmetric Allylic Alkylation......Page 112
Catalytic Substitution Reactions Involving Allylic Alkylation......Page 114
References......Page 116
Introduction......Page 123
Alkenes as Nucleophiles......Page 124
Enol Derivatives as Nucleophiles......Page 126
Allylic Metals as Nucleophiles......Page 129
Aromatic Compounds as Nucleophiles......Page 130
Radical Reaction......Page 132
New Method for the Nicholas Reaction......Page 133
Stoichiometric Propargylic Alkylation of Propargylic Alcohols Assisted by Ruthenium Complexes......Page 134
Ruthenium-catalyzed Reaction......Page 138
Rhenium-catalyzed Reaction......Page 145
Catalytic Benzylic Alkylation of Benzylic Alcohols and their Derivatives......Page 146
References......Page 149
Introduction......Page 151
Formation of Oxygen Ylide from Metal Carbene Complexes and Subsequent Reactions......Page 152
[2,3]-Sigmatropic rearrangement......Page 153
[1,2]-Shift (Stevens rearrangement) and related reactions......Page 157
1,3-Dipolar cycloaddition......Page 159
Asymmetric catalysis of 1,3-dipole addition of carbonyl ylides......Page 162
Miscellaneous reaction of carbonyl ylides......Page 163
Sulfur Ylide Formation and Subsequent Reactions......Page 164
[2,3]-Sigmatropic rearrangements......Page 165
Addition to C=O and C=N bonds......Page 166
Thiocarbonyl Ylide from Catalytic Reaction of alpha-Diazocarbonyl Compounds......Page 167
[2,3]-Sigmatropic rearrangements......Page 168
[1,2]-Shift (Stevens rearrangement) and Related Reactions......Page 169
Azomethine ylide and related reactions......Page 171
Reaction of Lewis Base with Nitrene or Metal Complexed Nitrene......Page 173
Concluding Remarks......Page 174
References......Page 175
Introduction......Page 179
Olefin Metathesis......Page 180
Heterocoupling versus Homocoupling in Olefin CM......Page 181
Stereoselective Olefin CM Reactions......Page 184
Styrene CM......Page 186
Preparation of Trisubstituted Olefins......Page 187
Reagent Synthesis by CM......Page 188
CM of Lewis-basic Substrates......Page 193
Summary of Substrate Scope - Olefin Chemoselectivity in CM......Page 195
Use of CM in One-Pot Sequential and Tandem Reactions......Page 197
Ethenolysis......Page 198
Additives to Prevent Olefin Migration in CM......Page 199
Summary......Page 200
References......Page 201
Introduction......Page 206
Carbacycles......Page 207
Cyclic ethers and lactones......Page 215
Alkaloids......Page 221
Carbacycles......Page 226
Alkaloids......Page 228
Lactones......Page 229
Cyclic ethers......Page 233
Formation of Macrocycles......Page 237
Macrolides......Page 238
Diene-Ene RCM......Page 244
Strained Compounds......Page 250
Ring-Rearrangement Reactions......Page 259
Metathesis on Solid Supports......Page 261
References......Page 264
Introduction......Page 269
Ring-Closing Metathesis......Page 272
Cross-Metathesis......Page 280
Tandem Cyclization (ROM-RCM, ROM-CM)......Page 284
Skeletal Reorganization with Metal Complex......Page 287
Enyne Metathesis for Synthesis of Natural Products and Biologically Active Substances......Page 293
Introduction......Page 296
Alkyne Metathesis with Tungsten Alkylidyne Complex......Page 299
Alkyne Metathesis Using Molybdenum Alkylidyne Complex......Page 302
References......Page 306
Introduction......Page 309
Intermolecular Couplings......Page 310
Intra-intermolecular Couplings......Page 312
Twofold Heck Couplings of 1,2-Dihalocycloalkenes and Related Compounds......Page 313
Other Alkenes......Page 315
Dienes and Trienes......Page 316
Inter-intramolecular Couplings......Page 318
Oligocyclizations Succeeding Inter- and Intramolecular Carbopalladations of Alkyne Triple Bonds......Page 320
Oligocyclizations Succeeding Inter- and Intramolecular Carbopalladations of Alkene Double Bonds......Page 323
Cyclizations Proceeding with Inter- and Intramolecular Carbopalladations of Allenes......Page 325
Cascade Cyclizations Involving C-H Bond Activation of an Arene......Page 326
Oligo- and Polymerizations by Heck Couplings......Page 329
References......Page 331
Pauson-Khand Reaction......Page 333
Problems in Association with the Proposed Mechanism......Page 334
Oxidative promoters......Page 335
Non-oxidative promoters......Page 336
Promotion by physical means......Page 337
Based on dicobalt octacarbonyl......Page 338
"Hard" Lewis base-modified cobalt catalysts......Page 339
Miscellaneous cobalt catalysts......Page 340
Homogeneous Catalysts Based on Metals Other than Cobalt......Page 341
Heterogenous (Immobilized) Catalysts......Page 342
Alternative Sources of CO......Page 343
Use of chiral auxiliary......Page 344
Chirality transfer from the substrates......Page 345
Use of chiral metal complexes......Page 346
Use of chiral catalysts......Page 347
Ethylene......Page 349
Allenic substrates......Page 350
Electron-deficient substrates......Page 351
Substrates having removable tethers......Page 352
1,3-Dienes......Page 353
Substrates on solid support......Page 354
Tandem Approaches Coupled with Other Reactions......Page 355
Natural Product Synthesis......Page 357
References......Page 360
Introduction......Page 364
Nickel Catalysts......Page 365
Palladium Catalysts......Page 366
Platinum Catalysts......Page 367
Rhodium Catalysts......Page 369
Rhodium Catalysts......Page 371
Lanthanide Catalysts......Page 374
Lanthanide Metallocene Catalysts......Page 376
Palladium Catalysts......Page 380
Cyclization with C-Si Bond Formation......Page 384
Cyclization with Si-O Bond Formation......Page 385
Cyclization/Silylation/Carbonylation of Diynes......Page 389
Cyclization/Silylformylation of Enynes......Page 391
Cascade Cyclization/Hydrosilylation of Trienes......Page 392
Cascade Cyclization/Hydrosilylation of Dieneynes......Page 394
Silane-initiated Cascade Cyclization of Triynes......Page 396
Silane-initiated Cascade Cyclization of Enediynes......Page 397
Cyclization/Disilylation......Page 398
Cyclization/Stannylsilylation......Page 399
Stannylative Cyclization......Page 402
Additional Processes Involving Tin, Boron, and Germanium......Page 404
References......Page 406
Carbonylative Cross-coupling......Page 408
Organotin Compounds......Page 409
Organoboron Compounds......Page 411
Organozinc Compounds......Page 414
Organosilicon Compounds......Page 415
Reactions Initiated by Oxidative Addition of C-X Bonds......Page 416
Reactions Involving pi-Allylic Palladium Complexes......Page 423
Carbonylative Cyclizations Involving Enolizable CH-Acids......Page 426
References......Page 429
Introduction......Page 431
Mechanism of hydroformylation......Page 432
normal-Selective hydroformylation before 1993......Page 433
Asymmetric hydroformylation before 1993......Page 435
normal-Selective hydroformylation......Page 437
Other catalyst systems giving a high enantioselectivity......Page 440
New Reaction Media and Catalysts for Separation......Page 443
Water......Page 445
Ionic liquid......Page 446
Polymer-supported catalyst......Page 447
Dendritic catalyst......Page 448
Supercritical carbon dioxide......Page 449
In situ observation by high-pressure IR spectroscopy......Page 450
EXAFS (extended X-ray absorption fine structure)......Page 452
Diastereoselective hydroformylation for synthesis of natural products and pharmaceuticals......Page 454
Sequential, cascade, and tandem reactions to construct complex structures......Page 458
Asymmetric Hydrocarbonylation......Page 460
Mechanism of Oxidative Alkoxycarbonylation......Page 462
References......Page 463
Introduction......Page 468
Catalyst and Solvents for Silylformylation......Page 469
1-Alkynes......Page 470
Chemoselectivity in Silylformylation of Terminal Acetylenes......Page 473
Internal Alkynes......Page 478
Mechanism of Silylformylation of Alkynes......Page 479
Silylformylation of Aldehydes, Epoxides, and Oxetanes......Page 483
Intramolecular Version of Silylformylation of Alkynes and Alkenes......Page 484
Silylative Lactonization of Alkynyl Alcohols......Page 488
Silylative Carbamoylation of Alkynes......Page 491
1,6-Diynes......Page 493
1,6-Enynes......Page 497
Cascade-Type Reactions in One-Pot Operation......Page 499
References......Page 503
Introduction......Page 506
Amidocarbonylation of Aldehydes......Page 507
Amidocarbonylation of Enamides......Page 509
Cyclohydrocarbonylation of Alkenes......Page 510
Cyclohydrocarbonylation of Alkynes......Page 517
Aminocarbonylation of Alkenyl and (Hetero)Aryl Halides......Page 522
Aminocarbonylation of Alkynes......Page 526
Aminocarbonylation Reactions without Using Gaseous Carbon Monoxide......Page 529
Intramolecular Aminocarbonylation Reactions......Page 531
Ring Expansion of Aziridines......Page 533
Ring Expansion of Pyrrolidines......Page 535
Ring Expansion via Rearrangement of Nitrogen Heterocycles......Page 536
Reductive Carbonylation Reactions......Page 538
Thiocarbonylation Reactions......Page 539
Carbonylation Reactions in Supercritical CO2......Page 542
Carbonylation Reactions in Ionic Liquids......Page 543
Radical Carbonylation Reactions......Page 544
Carbonylation Reactions with Microwave Irradiation......Page 546
References......Page 547
Introduction......Page 551
Polymerization of Monosubstituted Acetylenes......Page 553
Polymerization of Disubstituted Acetylenes......Page 560
Metal halide-based catalysts......Page 563
Metal carbonyl-based catalysts......Page 564
Nb and Ta Catalysts......Page 565
Rh Catalysts......Page 566
Controlled Polymerizations......Page 568
Living polymerization by single-component metal carbene catalysts......Page 570
Stereospecific Living Polymerization by Rh Catalysts......Page 571
Gas-permeable Polyacetylenes......Page 575
Helical Polyacetylenes......Page 577
Photoelectronically Functional Polyacetylenes......Page 582
References......Page 583
Introduction......Page 588
Regio- and Stereoregularities......Page 589
Homopolymerization of Epoxides......Page 590
Anionic polymerization......Page 591
Aluminum-Porphyrin/Lewis Acid Catalyst System......Page 592
Aluminum-Tetradentate Ligand Catalyst System......Page 594
Aluminate/Lewis Acid Catalyst System......Page 595
Cationic Aluminum Catalyst System......Page 596
Other Aluminum-based Catalyst Systems......Page 597
Zinc-based Catalyst System......Page 598
Catalyst System for the Alternating Co-polymerization......Page 599
Mechanistic Aspects......Page 601
Mechanistic Aspects......Page 602
Diphenoxyzinc complex......Page 603
Zinc-beta-diiminate (zinc-BDI) complex......Page 604
Cobalt Catalyst System......Page 607
Chromium Catalyst System......Page 608
Manganese Catalyst System......Page 610
Asymmetric Co-polymerization of Epoxides with CO2......Page 611
References......Page 613
Introduction......Page 615
Initiators Based on Transition Metals Other than Mo, W, and Ru......Page 616
Group 6 Initiators......Page 619
Group 8 Initiators......Page 621
Monomer Architecture and Functionality......Page 629
Controlling Molecular Weights......Page 631
Hybrid and Modified ROMP Polymers......Page 633
Modification of Endgroups......Page 634
Modification of Pendant Groups......Page 636
Applications......Page 637
References......Page 638
The Reaction with Grignard and Organozinc Reagents (Kumada-Tamao and Negishi Coupling)......Page 645
Reaction with Organotin Reagents (Migita-Kosugi-Stille Coupling)......Page 648
Reaction with Organoboron Reagents (Suzuki-Miyaura Coupling)......Page 652
Reaction with Organosilicon Reagents (Hiyama Coupling)......Page 660
Polymerization by Sonogashira-Hagihara Coupling......Page 662
Polymerization with Alkynylmetal Reagents......Page 665
Cross-coupling Polymerization with Organometallic Reagents of sp3-Hybridized Carbons......Page 668
Miscellaneous Cross-coupling Polymerizations......Page 670
References......Page 680
Polymerization of Alkenes......Page 683
Formation of Ion Pairs (Active Species)......Page 684
A latent vacant site in ISIPs and OSIPs......Page 686
Counteranion (Y-) and alternative stabilization (Z)......Page 687
Alkene Coordination and Insertion......Page 689
Polymerization Mechanisms of (alpha-Diimine)Ni and Pd Catalysts......Page 691
Branched Structure......Page 693
General considerations......Page 695
Syndioselective metallocenes......Page 696
Epimerization......Page 697
Stereoselective propylene polymerization with non-metallocene catalysts......Page 699
Ethylene monomer......Page 701
alpha-Olefin monomers......Page 703
Stereoselective Living Polymerization of alpha-Olefins......Page 705
Molecular Weight......Page 707
Co-polymers......Page 708
Polystyrene and Related Polymers......Page 711
Polybutadiene and Related Polymers......Page 712
Co-polymers of CO and Olefins......Page 713
Functionalized Polyolefins......Page 714
Co-polymerization of hydrocarbon monomers with polar monomers......Page 715
Chain-transfer reaction to a reactive chain-transfer agent......Page 716
Other methods......Page 717
Heterogenization of Soluble Single-site Catalysts......Page 718
Combinatorial Approach for Finding New Catalysts......Page 719
References......Page 720