Metal Vinylidenes and Allenylidenes in Catalysis: From Reactivity to Applications in Synthesis

Cover Page......Page 1
Title: Metal Vinylidenes and Allenylidenes in Catalysis......Page 6
ISBN 3527318925......Page 7
1 Preparation and Stoichiometric Reactivity of Mononuclear Metal Vinylidene Complexes......Page 8
2 Preparation and Stoichiometric Reactivity of Metal Allenylidene Complexes......Page 9
4 Theoretical Aspects of Metal Vinylidene and Allenylidene Complexes......Page 10
6 Ruthenium Vinylidenes in the Catalysis of Carbocyclization......Page 11
7 Allenylidene Complexes in Catalysis......Page 12
9 Rhodium and Group 9-11 Metal Vinylidenes in Catalysis......Page 13
Index......Page 14
Preface......Page 16
List of Contributors......Page 18
1.1 Introduction......Page 22
1.2.1 From 1-Alkynes......Page 23
1.2.1.1 Migration of Other Groups (SiR(3), SnR(3), SR, SeR)......Page 26
1.2.3 From Metal Alkynyls......Page 27
1.2.3.1 Some Specific Examples......Page 29
1.2.3.2 Redox Rearrangements of Metal Alkynyls and Vinylidenes......Page 30
1.2.5 From Metal-Carbyne Complexes......Page 32
1.2.6 From Metal-Carbon Complexes......Page 35
1.2.8 From Vinyls......Page 36
1.2.10 Miscellaneous Reactions Affording Vinylidenes......Page 37
1.2.11 Vinylvinylidene Complexes......Page 38
1.3 Stoichiometric Reactions......Page 40
1.3.1.2 Group 16 Nucleophiles. Oxygen......Page 41
1.3.1.4 Sulfur......Page 42
1.3.1.9 Hydride......Page 43
1.3.2.1 Formation of Cyclopropenes......Page 44
1.3.2.3 Coupling......Page 45
1.3.3 Reactions at C(β)......Page 46
1.3.3.1 Protonation......Page 47
1.3.4 Cycloaddition Reactions......Page 48
1.3.5 Adducts with Other Metal Fragments......Page 49
1.3.6 Ligand Substitution......Page 51
1.3.7 Miscellaneous Reactions......Page 52
1.4.1 Reactions of Ti(=C=CH(2))Cp*(2)......Page 54
1.4.2 Complexes Derived From Li[M(C CR)(CO)(NO)Cp] (M=Cr, W)......Page 55
1.4.3 Reactions of M(=C=CRR')(CO)(5) (M = Cr, Mo, W)......Page 56
1.4.4 Reactions of M(=C=CRR')(CO)(L) Cp (M = Mn, Re)......Page 58
1.4.6 Reactions of [Ru{=C=C(SMe)(2)}(PMe(3))(2)Cp](+)......Page 60
1.4.7 Reactions of trans-MCl(=C=CRR')(L)(2) (M=Rh, Ir)......Page 62
1.5 Reactions Supposed to Proceed via Metal Vinylidene Complexes......Page 63
Abbreviations......Page 66
References......Page 67
2.1 Introduction......Page 82
2.2.1 General Methods of Synthesis......Page 83
2.2.2 Group 6 Metals......Page 84
2.2.3 Group 7 Metals......Page 85
2.2.4 Group 8 Metals......Page 86
2.2.4.2 Half-Sandwich Derivatives......Page 87
2.2.5 Group 9 Metals......Page 89
2.4.1 General Considerations of Reactivity......Page 90
2.4.2 Electrophilic Additions......Page 91
2.4.3 Nucleophilic Additions......Page 92
2.4.3.1 Group 6 Metal-Allenylidenes......Page 93
2.4.3.2 Group 7 Metal-Allenylidenes......Page 94
2.4.3.3 Group 8 Metal-Allenylidenes......Page 95
2.4.3.4 Group 9 Metal-Allenylidenes......Page 99
2.4.4 C–C Couplings......Page 100
2.4.5.1 Reactions Involving the M=C(α) Bond......Page 102
2.4.5.2 Reactions Involving the C(α)=C(β) Bond......Page 103
2.4.5.3 Reactions Involving the C(β)=C(γ) Bond......Page 105
2.4.5.4 Reactions Involving Both C(α)=C(β) and C(β)=C(γ) Bonds (1,2,3-Heterocyclizations)......Page 108
2.4.6 Other Reactions......Page 110
2.5 Concluding Remarks......Page 111
References......Page 112
3.1 Introduction......Page 120
3.2 Steric and Electronic Structure......Page 121
3.3.1 Butatrienylidene Complex Synthesis......Page 124
3.3.2 Pentatetraenylidene Complex Synthesis......Page 129
3.3.4 Heptahexaenylidene Complex Synthesis......Page 134
3.4.1 Butatrienylidene Complexes......Page 135
3.4.2 Pentatetraenylidene Complexes......Page 140
3.4.4 Heptahexaenylidene Complexes......Page 144
3.5 Summary and Conclusion......Page 145
References......Page 146
4.1 Introduction......Page 150
4.2.1 Metal Vinylidene Complexes......Page 151
4.3 Barrier of Rotation of Vinylidene Ligands......Page 153
4.4.1 η(2)-Acetylene to Vinylidene......Page 155
4.4.2 Vinylidene to η(2)-Acetylene......Page 160
4.5 Reversible C–C σ-bond Formation by Dimerization of Metal Vinylidene Complexes......Page 162
4.6.1 Alkynol Cycloisomerization Promoted by Group 6 Metal Complexes......Page 163
4.6.2 Unusual Intramolecular [2 + 2] Cycloaddition of a Vinyl Group with a Vinylidene C=C Bond......Page 169
4.6.3 Intramolecular Methathesis of a Vinyl Group with a Vinylidene C=C Double Bond......Page 170
4.7 Heavier Group 14 Analogs of Metal Vinylidene Complexes......Page 171
4.8 Allenylidene Complexes......Page 172
4.9 Summary......Page 173
References......Page 174
5.2 Preparation of Fischer-type Carbene Complexes through the Generation of the Vinylidene Complexes......Page 180
5.3 Utilization of Pentacarbonyl Vinylidene Complexes of Group 6 Metals for Synthetic Reactions......Page 185
5.3.1 Catalytic Addition of Hetero-Nucleophiles......Page 186
5.3.2 Catalytic Addition of Carbo-Nucleophiles......Page 193
5.3.3 Electrocyclization and Related Reactions......Page 199
5.4 Utilization of Vinylidene to Alkyne Conversion......Page 205
5.5 Synthetic Reactions Utilizing Other Kinds of Vinylidene Complexes of Group 6 Metals......Page 207
5.6 Conclusion......Page 208
References......Page 209
6.2 Stoichiometric Carbocyclization via Ruthenium Vinylidene......Page 214
6.3.1 Cyclization of cis-3-En-1-Ynes......Page 216
6.3.2 Cycloaromatization of 3,5-Dien-1-Ynes......Page 217
6.3.3 Ruthenium-Catalyzed Cyclization of 3-Azadienynes......Page 223
6.3.4 Cycloisomerization of cis-1-Ethynyl-2-Vinyloxiranes......Page 224
6.3.5 Catalytic Cyclization of Enynyl Epoxides......Page 225
6.4.1 Cyclocarbonylation of 1,1'-Bis(silylethynyl)ferrocene......Page 229
6.4.3 Ruthenium-Catalyzed Cycloaddition Reaction between Enyne and Alkene......Page 230
6.6 Ruthenium-Catalyzed Hydrative Cyclization of 1,5-Enynes......Page 232
6.7 Carbocyclization Initiated by Addition of C-Nucleophile to Ruthenium Vinylidene......Page 234
References......Page 235
7.1 Introduction......Page 238
7.2.1 Propargylic Substitution Reactions with Heteroatom-Centered Nucleophiles......Page 240
7.2.2 Propargylic Substitution Reactions with Carbon-Centered Nucleophiles......Page 244
7.2.3 Reaction Pathway for Propargylic Substitution Reactions......Page 245
7.2.4 Asymmetric Propargylic Alkylation with Acetone......Page 248
7.2.5 Cycloaddition between Propargylic Alcohols and Cyclic 1,3-Dicarbonyl Compounds......Page 252
7.3.1 Propargylation of Heteroaromatic and Aromatic Compounds with Propargylic Alcohols......Page 254
7.3.2 Cycloaddition between Propargylic Alcohols and Phenol and Naphthol Derivatives......Page 255
7.4 Carbon–Carbon Bond Formation via Allenylidene-Ene Reactions......Page 257
7.5 Reductive Coupling Reaction via Hydroboration of Allenylidene Intermediates......Page 259
7.6 Selective Preparation of Conjugated Enynes......Page 260
7.7 Preparation of Dicationic Chalcogenolate-Bridged Diruthenium Complexes and Their Dual Catalytic Activity......Page 262
7.8 Other Catalytic Reactions via Allenylidene Complexes as Key Intermediates......Page 264
7.9 Conclusion......Page 267
References......Page 268
8.1 Introduction......Page 272
8.2.1 Allenylidene-Ruthenium Complexes as Alkene Metathesis Catalyst Precursors: the First Evidence......Page 273
8.2.2.2 Enyne Metathesis......Page 275
8.2.2.3 ROMP Promoted by Allenylidene Complexes......Page 276
8.2.3.1 The First Evidence......Page 277
8.2.3.2 The Intramolecular Allenylidene to Indenylidene Rearrangement Demonstration......Page 280
8.2.3.3 Applications of Isolated Indenylidene-Ruthenium Complexes in ROMP......Page 282
8.2.4 Propargylic Ethers as Alkene Metathesis Initiator Precursors: Generation of Alkenyl Alkylidene-Ruthenium Catalysts......Page 283
8.3.1 Preparation of Indenylidene-Ruthenium Catalysts......Page 286
8.3.2 Ruthenium Indenylidene Complexes in Alkene Metathesis......Page 289
8.3.3 Polymerization with Ruthenium Indenylidene Complexes......Page 292
8.3.4 Other Catalytic Reactions Promoted by Indenylidenes......Page 294
References......Page 295
9.1 Introduction......Page 300
9.2.1 Introduction......Page 301
9.2.2 Carbocyclization/Pericyclic Reactions......Page 302
9.2.3 Anti-Markovnikov Hydrofunctionalization......Page 309
9.2.4 Multi-Component Coupling......Page 315
9.3 Rhodium Alkenylidenes in Catalysis......Page 320
9.4.2 Nickel Vinylidenes in Catalysis......Page 323
9.4.3 Palladium Vinylidenes in Catalysis......Page 324
9.4.4 Platinum Vinylidenes in Catalysis......Page 325
9.4.5 Copper Vinylidenes in Catalysis......Page 327
9.4.6 Gold Vinylidenes in Catalysis......Page 328
9.6 Note Added in Proof......Page 331
References......Page 332
10.1 Introduction......Page 334
10.2.1 Addition of Carbamic Acids: Synthesis of Vinylic Carbamates and Ureas......Page 335
10.2.2 Addition of Carboxylic Acids: Synthesis of Enol Esters......Page 337
10.2.3 Addition of Water: Synthesis of Aldehydes......Page 339
10.2.4.2 Intermolecular Addition with Rearrangement: Formation of Unsaturated Ketones......Page 342
10.2.4.3 Intramolecular Addition: Formation of Cyclic Enol Ethers and Lactones from Pent-4-yn-1-ols and But-3-yn-1-ols......Page 344
10.3.2 Formation of Nitriles via Addition of Hydrazines to Terminal Alkynes......Page 346
10.4 Hydrophosphination: Synthesis of Vinylic Phosphine......Page 347
10.5 C–C Bond Formation: Dimerization of Terminal Alkynes......Page 348
10.6 Conclusion......Page 350
References......Page 351
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