Metal vinylidenes and allenylidenes in catalysis : from reactivity to applications in synthesis

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Publication Information:

Weinheim : Wiley, 2008

Physical Description:

xvii, 338 p. : ill. ; 25 cm.

ISBN:

9783527318926

Subject Term:

Catalysis

Organometallic compounds

Added Author:

Bruneau, Christian

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Library	Item Barcode	Call Number	Material Type	Item Category 1	Status
Searching... PSZ JB	30000010207456	QD505 M475 2008	Open Access Book	Book	Searching... Unknown

Focusing on preparation and applications in synthesis and catalysis, this book finally closes a gap in the literature by summarizing this hot topic for the first time.
As such, it gathers in one volume the key features of metal vinylidene and allenylidene complexes as well as reactive species and covers applications in metathesis, polymerization, molecular materials, carbon rich compounds and fine chemical production. The emphasis here is on the selective transformations of alkynes and enynes plus simple and complex molecules containing a triple C-C bond.
The result is a must-have ready reference for organic, catalytic, complex, theoretical and polymer chemists, as well as those working with/on organometallics.

Author Notes

Pierre H. Dixneuf, professor at the University of Rennes has been the head of the CNRS research Unit 6509 in Rennes (1986-1999), and he created the Institute of Chemistry in Rennes in 2000. He was research advisor at the University of Rennes (2001-04) and at CNRS chemistry headquarters (1996-99).
He obtained his academic degrees, PhD and habilitation, in Rennes was on leave of absence with professor M. F. Lappert, University of Sussex for one year. He innovated first in organometallic chemistry and then in homogeneous catalysis and conjugated carbon-rich systems. He has authored over 330 publications of which 70 in the last 5 years.
He has received several research awards : Le Bel (SFC), Grignard-Wittig (GDCh), Sacconi (Italy 2006), Académie des Sciences grand prix (2006).

Dr. Christian Bruneau is the head of the CNRS-University research group "Catalysis and Organometallics" in Rennes. He graduated in Chemistry from the Institut National Supérieur de Chimie Industrielle de Rouen in 1974, and obtained his Doctorate degree at the ENSCR national school of Rennes. Since 1986, he has been developing his research activities in the field of molecular organometallic catalysis. He is strongly involved in ruthenium-catalyzed selective transformations of alkynes, alkenes and enynes, cycloisomerization, rearrangement, and addition reactions. He is developing a topic on enantioselective reactions, mainly hydrogenation and allylic substitution with transition metal catalysts.

Michael I. BruceVictorio Cadierno and Pascale Crochet and Jose GimenoHelmut FischerJun Zhu and Zhenyang LinNobuharu IwasawaArjan Odedra and Rai-Shung LiuYoshiaki Nishibayashi and Sakae UemuraRaluca Malacea and Pierre H. DixneufSean H. Wiedemann and Chulbom LeeChristian Bruneau

Preface	p. XIII
List of Contributors	p. XV
1 Preparation and Stoichiometric Reactivity of Mononuclear Metal Vinylidene Complexes	p. 1
1.1 Introduction	p. 1
1.2 Preparative Methods	p. 2
1.2.1 From 1-Alkynes	p. 2
1.2.1.1 Migration of Other Groups (SiR[subscript 3], SnR[subscript 3], SR, SeR)	p. 5
1.2.2 The [eta superscript 2]-Alkyne to Hydrido([eta superscript 1]-Alkynyl) to Vinylidene Transformation	p. 6
1.2.3 From Metal Alkynyls	p. 6
1.2.3.1 Some Specific Examples	p. 8
1.2.3.2 Redox Rearrangements of Metal Alkynyls and Vinylidenes	p. 9
1.2.4 From Metal Allenylidenes via Metal Alkynyls	p. 11
1.2.5 From Metal-Carbyne Complexes	p. 11
1.2.6 From Metal-Carbon Complexes	p. 14
1.2.7 From Acyl Complexes	p. 15
1.2.8 From Vinyls	p. 15
1.2.9 From Alkenes	p. 16
1.2.10 Miscellaneous Reactions Affording Vinylidenes	p. 16
1.2.11 Vinylvinylidene Complexes	p. 17
1.3 Stoichiometric Reactions	p. 19
1.3.1 Reactions at C[subscript alpha]	p. 20
1.3.1.1 Deprotonation	p. 20
1.3.1.2 Group 16 Nucleophiles. Oxygen	p. 20
1.3.1.3 Alcohols	p. 21
1.3.1.4 Sulfur	p. 21
1.3.1.5 Group 15 Nucleophiles. Nitrogen	p. 22
1.3.1.6 Phosphorus	p. 22
1.3.1.7 Halogen Nucleophiles	p. 22
1.3.1.8 Carbon Nucleophiles	p. 22
1.3.1.9 Hydride	p. 22
1.3.2 Intramolecular Reactions	p. 23
1.3.2.1 Formation of Cyclopropenes	p. 23
1.3.2.2 Attack on Coordinated Phosphines	p. 24
1.3.2.3 Coupling	p. 24
1.3.2.4 Vinylidene/Alkyne Coupling	p. 25
1.3.2.5 Formation of [pi]-Bonded Ligands	p. 25
1.3.3 Reactions at C[subscript beta]	p. 25
1.3.3.1 Protonation	p. 26
1.3.3.2 Alkylation	p. 27
1.3.3.3 Other Electrophiles	p. 27
1.3.4 Cycloaddition Reactions	p. 27
1.3.5 Adducts with Other Metal Fragments	p. 28
1.3.6 Ligand Substitution	p. 30
1.3.7 Miscellaneous Reactions	p. 31
1.4 Chemistry of Specific Complexes	p. 33
1.4.1 Reactions of Ti(=C=CH[subscript 2])Cp*[subscript 2]	p. 33
1.4.2 Complexes Derived From Li[M(C identical with CR)(CO)(NO)Cp] (M=Cr, W)	p. 34
1.4.3 Reactions of M(=C=CRR')(CO)[subscript 5] (M = Cr, Mo, W)	p. 35
1.4.4 Reactions of M(=C=CRR')(CO)(L) Cp (M = Mn, Re)	p. 37
1.4.5 Reactions of [M(=C=CRR')(L')(P)Cp' superscript +] (M = Fe, Ru, Os)	p. 39
1.4.6 Reactions of [Ru{{=C=C(SMe)[subscript 2]}}(PMe[subscript 3])subscript 2 Cp superscript +]	p. 39
1.4.7 Reactions of trans-MCl(=C=CRR')(L)[subscript 2] (M=Rh, Ir)	p. 41
1.5 Reactions Supposed to Proceed via Metal Vinylidene Complexes	p. 42
Abbreviations	p. 45
References	p. 46
2 Preparation and Stoichiometric Reactivity of Metal Allenylidene Complexes	p. 61
2.1 Introduction	p. 61
2.2 Preparation of Allenylidene Complexes	p. 62
2.2.1 General Methods of Synthesis	p. 62
2.2.2 Group 6 Metals	p. 63
2.2.3 Group 7 Metals	p. 64
2.2.4 Group 8 Metals	p. 65
2.2.4.1 Octahedral and Five-Coordinate Derivatives	p. 66
2.2.4.2 Half-Sandwich Derivatives	p. 66
2.2.4.3 Other Synthetic Methodologies	p. 68
2.2.5 Group 9 Metals	p. 68
2.3 Coordination Models and Structural Features	p. 69
2.4 Stoichiometric Reactivity of Allenylidenes	p. 69
2.4.1 General Considerations of Reactivity	p. 69
2.4.2 Electrophilic Additions	p. 70
2.4.3 Nucleophilic Additions	p. 71
2.4.3.1 Group 6 Metal-Allenylidenes	p. 72
2.4.3.2 Group 7 Metal-Allenylidenes	p. 73
2.4.3.3 Group 8 Metal-Allenylidenes	p. 74
2.4.3.4 Group 9 Metal-Allenylidenes	p. 78
2.4.4 C-C Couplings	p. 79
2.4.5 Cycloaddition and Cyclization Reactions	p. 81
2.4.5.1 Reactions Involving the M=C[subscript alpha] Bond	p. 81
2.4.5.2 Reactions Involving the C[alpha]=C[subscript beta] Bond	p. 82
2.4.5.3 Reactions Involving the C[subscript beta]=C[subscript gamma] Bond	p. 84
2.4.5.4 Reactions Involving Both C[subscript alpha]=C[subscript beta] and C[subscript beta]=C[subscript gamma] Bonds (1,2,3-Heterocyclizations)	p. 87
2.4.6 Other Reactions	p. 89
2.5 Concluding Remarks	p. 90
References	p. 91
3 Preparation and Reactivity of Higher Metal Cumulenes Longer than Allenylidenes	p. 99
3.1 Introduction	p. 99
3.2 Steric and Electronic Structure	p. 100
3.3 Synthesis of Cumulenylidene Complexes	p. 103
3.3.1 Butatrienylidene Complex Synthesis	p. 103
3.3.2 Pentatetraenylidene Complex Synthesis	p. 108
3.3.3 Hexapentaenylidene Complex Synthesis	p. 113
3.3.4 Heptahexaenylidene Complex Synthesis	p. 113
3.4 Reactions of Higher Metal Cumulenes	p. 114
3.4.1 Butatrienylidene Complexes	p. 114
3.4.2 Pentatetraenylidene Complexes	p. 119
3.4.3 Hexapentaenylidene Complexes	p. 123
3.4.4 Heptahexaenylidene Complexes	p. 123
3.5 Summary and Conclusion	p. 124
References	p. 125
4 Theoretical Aspects of Metal Vinylidene and Allenylidene Complexes	p. 129
4.1 Introduction	p. 129
4.2 Electronic Structures of Metal Vinylidene and Allenylidene Complexes	p. 130
4.2.1 Metal Vinylidene Complexes	p. 130
4.2.2 Metal Allenylidene Complexes	p. 132
4.3 Barrier of Rotation of Vinylidene Ligands	p. 132
4.4 Tautomerization Between [eta superscript 2]-Acetylene and Vinylidene on Transition Metal Centers	p. 134
4.4.1 [eta superscript 2]-Acetylene to Vinylidene	p. 134
4.4.2 Vinylidene to [eta superscript 2]-Acetylene	p. 139
4.5 Reversible C-C [sigma]-bond Formation by Dimerization of Metal Vinylidene Complexes	p. 141
4.6 Metal Vinylidene Mediated Reactions	p. 142
4.6.1 Alkynol Cycloisomerization Promoted by Group 6 Metal Complexes	p. 142
4.6.2 Unusual Intramolecular [2 + 2] Cycloaddition of a Vinyl Group with a Vinylidene C=C Bond	p. 148
4.6.3 Intramolecular Methathesis of a Vinyl Group with a Vinylidene C=C Double Bond	p. 149
4.6.4 [2 + 2] Cycloaddition of Titanocene Vinylidene Complexes with Unsaturated Molecules	p. 150
4.7 Heavier Group 14 Analogs of Metal Vinylidene Complexes	p. 150
4.8 Allenylidene Complexes	p. 151
4.9 Summary	p. 152
References	p. 153
5 Group 6 Metal Vinylidenes in Catalysis (Cr, Mo, W)	p. 159
5.1 Introduction	p. 159
5.2 Preparation of Fischer-type Carbene Complexes through the Generation of the Vinylidene Complexes	p. 159
5.3 Utilization of Pentacarbonyl Vinylidene Complexes of Group 6 Metals for Synthetic Reactions	p. 164
5.3.1 Catalytic Addition of Hetero-Nucleophiles	p. 165
5.3.2 Catalytic Addition of Carbo-Nucleophiles	p. 172
5.3.3 Electrocyclization and Related Reactions	p. 178
5.4 Utilization of Vinylidene to Alkyne Conversion	p. 184
5.5 Synthetic Reactions Utilizing Other Kinds of Vinylidene Complexes of Group 6 Metals	p. 186
5.6 Conclusion	p. 187
References	p. 188
6 Ruthenium Vinylidenes in the Catalysis of Carbocyclization	p. 193
6.1 Introduction	p. 193
6.2 Stoichiometric Carbocyclization via Ruthenium Vinylidene	p. 193
6.3 Catalytic Carbocyclization via Electrocyclization of Ruthenium-Vinylidene Intermediates	p. 195
6.3.1 Cyclization of cis-3-En-1-Ynes	p. 195
6.3.2 Cycloaromatization of 3,5-Dien-1-Ynes	p. 196
6.3.3 Ruthenium-Catalyzed Cyclization of 3-Azadienynes	p. 202
6.3.4 Cycloisomerization of cis-1-Ethynyl-2-Vinyloxiranes	p. 203
6.3.5 Catalytic Cyclization of Enynyl Epoxides	p. 204
6.4 Catalytic Carbocyclization via Cycloaddition of Ruthenium Vinylidene Intermediates	p. 208
6.4.1 Cyclocarbonylation of 1,1'-Bis(silylethynyl)ferrocene	p. 208
6.4.2 Dimerization of 1-Arylethynes to 1-Aryl-Substituted Naphthalenes	p. 209
6.4.3 Ruthenium-Catalyzed Cycloaddition Reaction between Enyne and Alkene	p. 209
6.5 Catalyzed Cyclization of Alkynals to Cycloalkenes	p. 211
6.6 Ruthenium-Catalyzed Hydrative Cyclization of 1,5-Enynes	p. 211
6.7 Carbocyclization Initiated by Addition of C-Nucleophile to Ruthenium Vinylidene	p. 213
6.8 Conclusion	p. 214
References	p. 214
7 Allenylidene Complexes in Catalysis	p. 217
7.1 Introduction	p. 217
7.2 Propargylic Substitution Reactions	p. 219
7.2.1 Propargylic Substitution Reactions with Heteroatom-Centered Nucleophiles	p. 219
7.2.2 Propargylic Substitution Reactions with Carbon-Centered Nucleophiles	p. 223
7.2.3 Reaction Pathway for Propargylic Substitution Reactions	p. 224
7.2.4 Asymmetric Propargylic Alkylation with Acetone	p. 227
7.2.5 Cycloaddition between Propargylic Alcohols and Cyclic 1,3-Dicarbonyl Compounds	p. 231
7.3 Propargylation of Aromatic Compounds with Propargylic Alcohols	p. 233
7.3.1 Propargylation of Heteroaromatic and Aromatic Compounds with Propargylic Alcohols	p. 233
7.3.2 Cycloaddition between Propargylic Alcohols and Phenol and Naphthol Derivatives	p. 234
7.4 Carbon-Carbon Bond Formation via Allenylidene-Ene Reactions	p. 236
7.5 Reductive Coupling Reaction via Hydroboration of Allenylidene Intermediates	p. 238
7.6 Selective Preparation of Conjugated Enynes	p. 239
7.7 Preparation of Dicationic Chalcogenolate-Bridged Diruthenium Complexes and Their Dual Catalytic Activity	p. 241
7.8 Other Catalytic Reactions via Allenylidene Complexes as Key Intermediates	p. 243
7.9 Conclusion	p. 246
References	p. 247
8 Ruthenium Allenylidenes and Indenylidenes as Catalysts in Alkene Metathesis	p. 251
8.1 Introduction	p. 251
8.2 Propargyl Derivatives as Alkene Metathesis Initiator Precursors: Allenylidenes, Indenylidenes and Alkenylalkylidenes	p. 252
8.2.1 Allenylidene-Ruthenium Complexes as Alkene Metathesis Catalyst Precursors: the First Evidence	p. 252
8.2.2 Allenylidene-Ruthenium Complexes in RCM, Enyne Metathesis and ROMP	p. 254
8.2.2.1 RCM Reactions	p. 254
8.2.2.2 Enyne Metathesis	p. 254
8.2.2.3 ROMP Promoted by Allenylidene Complexes	p. 255
8.2.3 Indenylidene-Ruthenium Complexes: the Alkene Metathesis Catalytic Species from Allenylidene Ruthenium Complexes	p. 256
8.2.3.1 The First Evidence	p. 256
8.2.3.2 The Intramolecular Allenylidene to Indenylidene Rearrangement Demonstration	p. 259
8.2.3.3 Applications of Isolated Indenylidene-Ruthenium Complexes in ROMP	p. 261
8.2.3.4 Indenylidene-Ruthenium(arene) Catalyst in Diene and Enyne RCM	p. 262
8.2.4 Propargylic Ethers as Alkene Metathesis Initiator Precursors: Generation of Alkenyl Alkylidene-Ruthenium Catalysts	p. 262
8.3 Indenylidene-Ruthenium Catalysts in Alkene Metathesis	p. 265
8.3.1 Preparation of Indenylidene-Ruthenium Catalysts	p. 265
8.3.2 Ruthenium Indenylidene Complexes in Alkene Metathesis	p. 268
8.3.3 Polymerization with Ruthenium Indenylidene Complexes	p. 271
8.3.4 Other Catalytic Reactions Promoted by Indenylidenes	p. 273
8.4 Conclusion	p. 274
References	p. 274
9 Rhodium and Group 9-11 Metal Vinylidenes in Catalysis	p. 279
9.1 Introduction	p. 279
9.2 Rhodium and Iridium Vinylidenes in Catalysis	p. 280
9.2.1 Introduction	p. 280
9.2.2 Carbocyclization/Pericyclic Reactions	p. 281
9.2.3 Anti-Markovnikov Hydrofunctionalization	p. 288
9.2.4 Multi-Component Coupling	p. 294
9.3 Rhodium Alkenylidenes in Catalysis	p. 299
9.4 Group 10 and 11 Metal Vinylidenes in Catalysis	p. 302
9.4.1 Introduction	p. 302
9.4.2 Nickel Vinylidenes in Catalysis	p. 302
9.4.3 Palladium Vinylidenes in Catalysis	p. 303
9.4.4 Platinum Vinylidenes in Catalysis	p. 304
9.4.5 Copper Vinylidenes in Catalysis	p. 306
9.4.6 Gold Vinylidenes in Catalysis	p. 307
9.5 Conclusion	p. 310
9.6 Note Added in Proof	p. 310
References	p. 311
10 Anti-Markovnikov Additions of O-, N-, P-Nucleophiles to Triple Bonds with Ruthenium Catalysts	p. 313
10.1 Introduction	p. 313
10.2 C-O Bond Formation	p. 314
10.2.1 Addition of Carbamic Acids: Synthesis of Vinylic Carbamates and Ureas	p. 314
10.2.2 Addition of Carboxylic Acids: Synthesis of Enol Esters	p. 316
10.2.3 Addition of Water: Synthesis of Aldehydes	p. 318
10.2.4 Addition of Alcohols: Synthesis of Ethers and Ketones	p. 321
10.2.4.1 Intermolecular Addition: Formation of Unsaturated Ethers and Furans	p. 321
10.2.4.2 Intermolecular Addition with Rearrangement: Formation of Unsaturated Ketones	p. 321
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	p. 323
10.3 Formation of C-N Bonds via Anti-Markovnikov Addition to Terminal Alkynes	p. 325
10.3.1 Addition of Amides to Terminal Alkynes	p. 325
10.3.2 Formation of Nitriles via Addition of Hydrazines to Terminal Alkynes	p. 325
10.4 Hydrophosphination: Synthesis of Vinylic Phosphine	p. 326
10.5 C-C Bond Formation: Dimerization of Terminal Alkynes	p. 327
10.6 Conclusion	p. 329
References	p. 330
Index	p. 333

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