Applications II. Transition Metal Compounds in Organic Synthesis 1

Comprehensive Organometallic Chemistry III.pdf......Page 1
Introduction......Page 3
Atropisomeric Biaryl Bisphosphine Ligands......Page 4
Chiral Bisphosphane Ligands on the Modification of DIOP......Page 9
Chiral Ferrocene-based Bisphosphane Ligands......Page 12
P-chiral Bisphosphane Ligands......Page 13
Other Bisphosphane Ligands......Page 15
Chelating Aminophosphine, Amidophosphine, and Phosphoramidites......Page 16
Chiral Monophosphorus Ligands......Page 18
Chiral N, P Ligands......Page 19
Hydrogenation of dehydroamino acid derivatives......Page 21
Hydrogenation of enamides......Page 28
Hydrogenation of (beta-acylamino) acrylates......Page 31
Hydrogenation of enol esters......Page 34
alpha,beta-Unsaturated carboxylic acids......Page 35
alpha,beta-Unsaturated esters, amides, lactones, and ketones......Page 37
Itaconic acids and their derivatives......Page 38
Hydrogenation of unsaturated alcohols......Page 39
Hydrogenation of unfunctionalized olefins......Page 41
alpha-Keto esters......Page 42
beta-Keto esters......Page 43
Amino ketones......Page 47
Hydroxyl ketones, alkoxy ketones, phenylthio ketones, and ortho-haloaryl ketones......Page 49
Diketones......Page 50
Keto phosphonates......Page 51
Aromatic ketones......Page 52
Aliphatic ketones......Page 55
Unsaturated ketones......Page 56
Asymmetric Hydrogenation of Imines......Page 57
Hydrogenation of acyclic aromatic imines......Page 58
Hydrogenation of cyclic imines......Page 60
Hydrogenation of C=N-X substrates......Page 61
References......Page 64
Allylamines......Page 73
Allylic Alcohols......Page 78
Allyl Ethers......Page 87
Other Alkenes......Page 95
Propargylic Alcohols......Page 97
References......Page 100
Introduction......Page 103
Organometallic aspects......Page 104
Synthetic aspects......Page 106
Intermolecular processes......Page 113
Intramolecular processes......Page 116
Functionalization of the C-H Bond of sp2- and sp-Hybridized Carbon Atoms......Page 123
Intermolecular Functionalization......Page 124
Intramolecular Functionalization......Page 132
Functionalization of Olefins......Page 157
Functionalization of Alkynes......Page 159
Application to Organic Syntheses......Page 161
References......Page 164
Introduction......Page 169
C-H Insertion of Alkanes......Page 170
Enolate alkylation equivalent......Page 173
Aldol reaction equivalent......Page 174
Mannich reaction equivalent......Page 176
Claisen rearrangement equivalent......Page 178
Combined C-H Activation/Cope Rearrangement......Page 179
Tandem Claisen rearrangement/Cope rearrangement equivalent......Page 180
Intramolecular Carbene C-H Insertion......Page 183
Carbene Precursors and Catalysts......Page 184
Lactam Formation......Page 187
Lactone Formation......Page 190
Cyclopentanone Formation......Page 193
Dihydrobenzofuran and Dihydrobenzopyran Formation......Page 195
Nitrene Precursors and Catalysts......Page 198
Manganese-catalyzed Nitrene C-H Insertion......Page 199
Ruthenium-catalyzed Nitrene C-H Insertion......Page 201
Intramolecular nitrene C-H insertion......Page 203
Applications in total synthesis......Page 205
Catalysis by Other Metals......Page 206
References......Page 209
Alkylation of C-H Bonds......Page 215
Alkenylation of C-H Bonds......Page 223
Arylation of C-H Bonds......Page 228
Carbonylation of C-H Bonds......Page 234
Hydroxylation and the Related Reactions......Page 240
Silylation of C-H Bonds......Page 241
Borylation of C-H Bonds......Page 243
Application......Page 244
References......Page 248
Introduction......Page 253
General Discussion......Page 257
Controlled monocarbometallation......Page 258
Formation and carbometallation of titanacyclopropanes and titanacyclopropenes......Page 261
Alkene-alkene coupling......Page 264
Alkyne-alkene coupling......Page 265
Controlled monocarbometallation of alkynes with Me3Al-ZrCp2Cl2......Page 269
Other Zr-catalyzed monocarbometallation reaction of alkynes......Page 273
Zirconium-catalyzed asymmetric carboalumination of alkenes (ZACA reaction)......Page 274
Cyclic carbometallation of organozirconium compounds......Page 278
Formation and characterization of zirconacyclopropanes and zirconacyclopropenes......Page 279
Catalytic carbozirconation proceeding via zirconacycles......Page 280
Other novel transformations of three- and five-membered zirconacycles......Page 281
Carbometallation of V......Page 285
Carbometallation Reactions of Group 6 Metals: Cr, Mo, and W......Page 286
Stoichiometric carbomanganation with well-defined organomanganese compounds......Page 288
Mn-catalyzed carbometallation......Page 291
Conclusion......Page 293
References......Page 294
Introduction......Page 300
Alkenes......Page 301
Alkynes......Page 303
Allenes......Page 310
Conia-ene......Page 313
Arylation of Carbonyl Compounds......Page 315
Intramolecular Carbopalladation......Page 317
Hydrovinylation......Page 319
Additions of Metallocarbenoids to Unsaturated Partners......Page 321
Enynes......Page 323
Metallacyclopentene pathway......Page 325
The pi-allyl pathway......Page 329
The vinylmetal pathway......Page 330
Hydrometallation......Page 332
Hydrostannylation......Page 334
Hydrosilylation and related reactions......Page 335
Carbometallation......Page 336
Skeletal rearrangements of enynes......Page 337
Dienes and Polyenes......Page 347
Polyenes......Page 351
Diynes......Page 352
Allenynes......Page 357
Allenenes......Page 360
References......Page 363
Introduction......Page 370
Organolithium Nucleophiles2,3......Page 371
Organomagnesium Nucleophiles......Page 372
Organocuprates with chiral non-transferable ligand......Page 374
Detailed mechanism......Page 375
2-cyclohexenones and larger rings......Page 376
2-Cyclopentenone substrate......Page 379
Addition to alpha,beta-unsaturated esters and amides......Page 380
Addition to nitroolefins......Page 383
Nickel-catalyzed conjugate addition to acyclic enones......Page 384
Addition to alpha,beta-unsaturated ketones......Page 385
Addition to alpha,beta-unsaturated esters and amides......Page 387
Diene ligands......Page 389
Organoaluminum Nucleophiles......Page 390
Organotin Nucleophiles......Page 392
Organosilicon Nucleophiles......Page 393
Organobismuth Nucleophiles......Page 396
Applications in Organic Synthesis......Page 397
Conclusion......Page 398
References......Page 399
C-C Bond Formation through Addition of C-M to C=O, C=N, and C&z.tbnd;N Bonds......Page 403
Addition to C=N......Page 405
Addition to C=O......Page 406
Addition to C=N......Page 409
Allylsamarium reagents......Page 410
Samarium enolates......Page 414
Ytterbium......Page 415
Titanium......Page 416
Addition to C=O......Page 417
Addition to C=N......Page 419
Zirconium......Page 421
Addition to C=O and C=N......Page 422
Hafnium......Page 424
Addition to C=O......Page 425
Niobium......Page 426
Addition to C&z.tbnd;N......Page 427
Addition to C=O......Page 428
Addition to C=N and C&z.tbnd;N......Page 429
Addition to C=O......Page 431
Addition to C=N......Page 432
Molybdenum......Page 433
Tungsten......Page 434
Manganese......Page 435
Addition to C=O......Page 436
Addition to C=O......Page 437
Addition to C=N......Page 438
Addition to C=O......Page 439
Addition to C=O and C=N......Page 440
Addition to C&z.tbnd;N......Page 444
Addition to C&z.tbnd;N......Page 445
Addition to C=O......Page 447
Addition to C=O......Page 448
Addition to C=N......Page 453
Addition to C=O......Page 455
Addition to C=O......Page 456
Addition to C&z.tbnd;N......Page 462
Addition to C=O and C=N......Page 463
Addition to C&z.tbnd;N......Page 468
Addition to C=O......Page 470
Copper......Page 471
Stoichiometric use of copper......Page 472
Catalytic use of copper......Page 474
Silver acetylenides......Page 476
Gold......Page 478
Addition to C=N......Page 479
References......Page 480
Introduction and Scope......Page 492
Early transition metal catalysts......Page 493
Group III and lanthanide catalysts......Page 496
Late transition metal catalysts......Page 497
Reductive Cyclization Involving Activated Alkenes......Page 500
Early transition metal, group III, and lanthanide catalysts......Page 503
Late transition metal catalysts......Page 505
Reductive Cyclization of 1,6- and 1,7-Diynes......Page 510
Reductive Cyclization of 1,6- and 1,7-Allenynes......Page 515
Reductive aldol cyclization......Page 516
Reductive cyclization of 1,3-dienyl carbonyl compounds......Page 521
Reductive Cyclization of Acetylenic and Allenic Carbonyl Compounds......Page 523
Reductive Cyclizations of Dicarbonyl Compounds (Pinacol and McMurry Couplings)......Page 528
Conclusion......Page 529
References......Page 531
Reaction with Acetylenes......Page 536
Reaction with Dienes......Page 540
Terminal acetylenes......Page 542
Internal acetylenes......Page 545
Benzynes......Page 547
Reaction with Dienes......Page 548
Reaction with Acetylenes......Page 550
Ru-mediated Reaction......Page 551
Pd-mediated Reaction......Page 552
References......Page 553
Introduction......Page 555
Lewis Acid-catalyzed Carbonyl-Ene Reactions......Page 556
Asymmetric Carbonyl-Ene Reactions......Page 557
Imino-Ene Reactions......Page 562
Transition Metal-Catalyzed Intermolecular Alder-Ene Reactions......Page 563
Palladium......Page 566
Ruthenium......Page 570
Rhodium......Page 573
Miscellaneous Metals......Page 574
Asymmetric Alder-ene Reactions......Page 577
Allenic Alder-Ene Reactions......Page 582
Applications of the Alder-Ene Reaction to the Synthesis of Biologically Relevant Compounds......Page 590
References......Page 597
Introduction......Page 600
Metal-catalyzed [5+2]-cycloadditions of vinylcyclopropanes and pi-systems......Page 602
Metal-mediated [5+2]-cycloadditions......Page 611
[4+3]-Cycloadditions......Page 613
[4+4]-Cycloadditions......Page 615
[6+2]- and [6+4]-Cycloadditions of trienes and pi-systems......Page 618
[6+2]-Cycloadditions of vinylcyclobutanones and pi-systems......Page 620
[6+3]-Cycloadditions......Page 621
[5+4]-Cycloadditions......Page 622
[4+2+1]-Cycloadditions......Page 623
[3+2+2]-Cycloadditions......Page 625
[5+2+1]-Cycloadditions......Page 628
[4+2+2]-Cycloadditions......Page 630
[5+2+2]-Cycloadditions......Page 633
[6+2+2]- and [6+2+2+2]-Cycloadditions......Page 634
[2+2+2+1]-Cycloadditions......Page 635
[5+2+1+1]-Cycloadditions......Page 638
Conclusion......Page 640
References......Page 641
Introduction......Page 645
Copper-mediated Cross-coupling Reactions......Page 646
Palladium-catalyzed Cross-coupling Reactions......Page 650
O-allylation of phenols......Page 653
O-allylation of aliphatic alcohols......Page 655
Allylation of other oxygen nucleophiles......Page 659
Etherification with Addition to the Central Carbon of a pi-Allyl Species......Page 660
Cobalt-mediated Propargylic Etherification......Page 661
Transition Metal-catalyzed Propargylic Etherification......Page 662
Etherification via Ring Opening of Epoxides......Page 665
Inter- and intramolecular hydroalkoxylation......Page 668
Cycloetherification with concomitant C-C bond formation using alkynes......Page 669
Addition of oxygen nucleophiles to alkynes via metal vinylidenes......Page 672
Transition metal-mediated hydration of alkynes......Page 674
Alkoxylation via Wacker-type reactions......Page 675
Wacker processes with subsequent carbonylation......Page 677
Wacker processes leading to pi-allyl intermediates......Page 678
Hydro- and alkylative alkoxylation......Page 679
Etherification by SN1 and SN2 Processes......Page 680
Etherification through C-H Bond Functionalization......Page 681
References......Page 682
Reaction with Allylic Alcohol Derivatives......Page 690
Reaction with Alkenyl Oxiranes and Aziridines......Page 699
Amination Through Cross-Coupling Reaction......Page 701
Reaction with Alkenes......Page 705
Reaction with Alkynes......Page 709
Reaction with Allenes......Page 712
Conclusion......Page 715
References......Page 716
C-E Bond Formation through Element-Element Addition to Carbon-Carbon Multiple Bonds......Page 720
Overview......Page 721
Addition to alkynes......Page 722
Addition to alkenes......Page 724
Addition to allenes......Page 725
Addition to activated alkenes......Page 726
Addition to carbenoids......Page 728
Addition to alkynes......Page 729
Addition to alkenes......Page 733
Addition to 1,3-dienes......Page 738
Addition to carbonyl compounds including enones and quinones......Page 740
Addition to methylenecylopropanes......Page 741
Addition to alkynes......Page 742
Addition to alkynes......Page 743
Addition to allenes......Page 745
Addition to alkynes......Page 746
Addition to alkynes......Page 747
Addition to alkenes......Page 750
Silaboration and germaboration of alkynes......Page 753
Silaboration of allenes......Page 755
Silaboration of 1,3-dienes......Page 757
Silaboration of vinylcyclopropanes and methylenecylopropanes......Page 759
Silaboration of isocyanides......Page 760
Silaboration of carbenoids......Page 761
Addition to alkynes......Page 762
Addition to 1,3-dienes......Page 763
Addition to allenes......Page 764
Addition to alkynes......Page 765
Addition to alkenes......Page 770
Addition to 1,3-dienes......Page 771
Addition to allenes......Page 772
Addition to alkynes......Page 773
Addition to alkynes......Page 774
Addition to alkynes......Page 775
Addition to alkynes......Page 776
References......Page 777
Introduction......Page 783
Mechanistic Aspects of Hydrosilylation......Page 784
Catalysis by Late Transition Metals: Groups 10 and 11......Page 787
Hydrosilylation with Group 9 Transition Metals......Page 790
Ruthenium and Iron Catalysis......Page 792
Early Transition Metals as Catalysts......Page 794
Yttrium catalysts for regiocontrol based on sterics......Page 795
Ruthenium catalysis......Page 796
Intramolecular cis-addition processes with platinum catalysts......Page 799
Intramolecular hydrosilylation catalyzed by ruthenium......Page 801
Additional Applications of Vinylsilanes......Page 802
Tandem Reductive Alkyne Silylation/C-C Bond Formation......Page 803
Conclusion......Page 804
References......Page 805
Mechanism of Transition Metal-Catalyzed Hydrosilylation of Alkenes......Page 808
Asymmetric Hydrosilylation of Styrene and its Derivatives......Page 810
Asymmetric Hydrosilylation of 1,3-Dienes......Page 817
Asymmetric Hydrosilylation of Alkyl-Substituted Acyclic Alkenes......Page 821
Asymmetric Hydrosilylation of Cyclic Alkenes......Page 823
Asymmetric Intramolecular Hydrosilylation......Page 825
Asymmetric Cyclization-Hydrosilylation......Page 826
References......Page 829
Hydroboration......Page 832
Mechanism......Page 834
Chemoselectivity......Page 835
Stereoselectivity......Page 837
Chiral P,P ligands......Page 838
Chiral P,N ligands......Page 845
Hydroalumination......Page 850
Mechanism......Page 851
Chemoselectivity......Page 852
Stereoselectivity......Page 854
Hydroboration......Page 857
Hydroalumination......Page 858
References......Page 860