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  Contents  
 
  Volume 1  
  Preface xxi
  References xxv
  List of Contributors xxvii
1.1 Introduction
Robert H. Grubbs 		1
  References 3
1.2 The Role of the "Tebbe Complex" in Olefin Metathesis
Robert H. Grubbs 		4
  References 6
1.3 The Discovery and Development of High Oxidation State Mo and W Imido Alkylidene Complexes for Alkene Metathesis
Richard R. Schrock 		8
1.3.1 Introduction 8
1.3.2 Tantalum Alkylidene Complexes 9
1.3.3 Early Tungsten Alkylidene Complexes 13
1.3.4 Development of Imido Alkylidene Complexes 15
1.3.5 Rhenium Alkylidene Complexes 20
1.3.6 Details of Reactions of Imido Alkylidene Complexes and Theoretical Calculations 21
1.3.7 Catalyst and Reaction Variations 24
1.3.8 Concluding Remarks 28
  Acknowledgments 28
  References 29
1.4 From Ill-Defined to Well-Defined W Alkylidene Complexes
Christophe Copéret, Frédéric Lefebvre, and Jean-Marie Basset 		33
1.4.1 Introduction 33
1.4.2 Oxoalkylidene W Complexes 33
1.4.3 Alkoxy-Alkylidene W Complexes: Kress-Osborn System 35
1.4.4 Aryloxy-Alkylidene W Complexes: Leconte-Basset System 37
1.4.5 Amidoalkylidene W Complexes 38
1.4.6 Imido-Alkylidene W Complexes: Schrock's System 42
1.4.7 Summary and Outlooks 44
  References 45
1.5 Fischer Metal Carbenes and Olefin Metathesis
Thomas J. Katz 		47
1.5.1 Fischer Metal Carbenes and Olefin Metathesis 47
1.5.2 The Role of Fischer Metal Carbenes in Metathesis 47
1.5.3 Induction of Olefin Metatheses by Fischer Metal Carbenes 49
1.5.3.1 Properties of 2 49
1.5.3.2 Olefin Metatheses Initiated by Metal Carbene 1 49
1.5.3.3 Mechanistic Implications 51
1.5.3.4 Metatheses Initiated by Metal Carbene 2 52
1.5.4 Initiation of Acetylene Polymerization by Fischer Metal Carbenes 53
1.5.4.1 Introduction 53
1.5.4.2 Examples of Acetylene Polymerizations Initiated by Fischer Metal Carbenes 54
1.5.5 Actuation of Olefin Metathesis by Acetylenes 55
1.5.5.1 Metatheses of Cyclic and Acyclic Alkenes Actuated by An Acetylene 55
1.5.5.2 Reaction of Enynes With Fischer Metal Carbenes 55
1.5.5.3 Rearrangement of Enynes to Dienes 56
  References 57
1.6 The Discovery and Development of Well-Defined, Ruthenium-Based Olefin Metathesis Catalysts
SonBinh T. Nguyen and Tina M. Trnka 		61
1.6.1 The Discovery of Well-Defined Ruthenium Olefin Metathesis Catalysts: A Personal Account by SonBinh Nguyen 61
1.6.1.1 (PPh3)2Cl2Ru=CH-CH=CPh2, the First Well-Defined, Metathesis-Active Ruthenium Alkylidene Complex 62
1.6.1.2 (PCy3)2Cl2Ru=CH-CH=CPh2, A Well-Defined Ruthenium Alkylidene Catalyst for the Metathesis of Acyclic Olefins 63
1.6.1.3 Initial Applications of Olefin Metathesis Chemistry Catalyzed by (PCy3)2Cl2Ru=CH-CH=CPh2 64
1.6.2 More Accessible Ruthenium Alkylidene Sources 65
1.6.3 2nd-Generation Grubbs Catalysts 68
1.6.3.1 N-Heterocyclic Carbene (NHC) Ligands 70
1.6.4 Multi-Component Ruthenium-Based Olefin Metathesis Catalyst Systems and Homogeneous Catalyst Precursors 73
1.6.5 Solid-Supported Ruthenium-Based Olefin Metathesis Catalysts 74
1.6.6 Conclusions 80
  References 81
1.7 Synthesis of Ruthenium Carbene Complexes
Warren R. Roper 		86
1.7.1 Introduction 86
1.7.2 The First Ruthenium Carbene Complexes 86
1.7.3 Ruthenium Methylene Complexes 88
1.7.4 Ruthenium Dihalocarbene Complexes 92
  Acknowledgments 93
  References 93
1.8 Synthesis of Rhodium and Ruthenium Carbene Complexes with a 16-Electron Count
Helmut Werner and Justin Wolf 		95
1.8.1 Introduction 95
1.8.2 Rhodium(I) Carbenes from Diazoalkanes 95
1.8.3 Ruthenium(II) Carbenes and Vinylidenes from Terminal Alkynes 98
1.8.4 Conclusions 108
  Acknowledgements 109
  References 109
1.9 Mechanism of Ruthenium-Catalyzed Olefin Metathesis Reactions
Melanie S. Sanford and Jennifer A. Love 		112
1.9.1 Introduction 112
1.9.2 First-Generation Bis-Phosphine Catalyst Systems 112
1.9.2.1 General Mechanistic Considerations 112
1.9.2.2 Substituent Effects in Ruthenium-Catalyzed Olefin Metathesis 116
1.9.2.3 Thermal Decomposition of Ruthenium Catalysts 118
1.9.2.4 Decomposition in the Presence of Functional Groups 120
1.9.2.5 Mechanistic Considerations in Other First-Generation Ruthenium Metathesis Catalysts 120
1.9.3 Second-Generation Ruthenium Olefin Metathesis Catalysts 123
1.9.3.1 General Mechanistic Considerations 124
1.9.3.2 Substituent Effects in Ruthenium-Catalyzed Olefin Metathesis 125
1.9.3.3 Thermal Decomposition of Ruthenium Catalysts 127
1.9.3.4 Decomposition in the Presence of Functional Groups 127
1.9.3.5 Other Second-Generation Ruthenium Catalysts 128
1.9.4 Conclusions 129
  References 130
1.10 Intrinsic Reactivity of Ruthenium Carbenes
Christian Adlhart and Peter Chen 		132
1.10.1 Introduction 132
1.10.2 Electrospray Ionization Mass Spectrometry (ESI MS) of Transition Metal Complexes 135
1.10.2.1 Electrospray Ionization 135
1.10.2.2 Tandem Mass Spectrometry 136
1.10.2.3 Reaction Conditions in the Collision Cell of the Tandem ESI MS 137
1.10.3 General Reactivity of Ruthenium Carbene Complexes in the Gas Phase 139
1.10.3.1 Dissociative Mechanism 139
1.10.3.2 Evidence for ROMP and RCM 141
1.10.3.3 Systematic Variation of a Common Structural Motif -- Steric Effects and Halogen Effects 143
1.10.3.4 Conclusions 146
1.10.4 Three Key Factors that Determine the Activity of Metathesis Catalysts 147
1.10.4.1 Solution-Phase Pre-Equilibria: Activation 147
1.10.4.2 Pre-Equilibria During the Turnover: Backbiting 148
1.10.4.3 Catalyst Commitment: Potential Surface 155
1.10.5 Conclusions 167
  Compound Numbers 167
  References 169
1.11 The Discovery and Development of High Oxidation State Alkylidyne Complexes for Alkyne Metathesis
Richard R. Schrock 		173
1.11.1 Introduction 173
1.11.2 Alkylidyne Complexes of Tantalum 174
1.11.3 Alkylidyne Complexes of Tungsten 174
1.11.4 Formation of Trialkoxy Alkylidyne Complexes from W2(OR)6 Species 178
1.11.5 Alkylidyne Complexes of Molybdenum 180
1.11.6 Reactions that Limit Metathesis Activity 181
1.11.7 Alkylidyne Complexes of Rhenium 185
1.11.8 Conclusions and Comments 186
  Acknowledgments 187
  References 187
1.12 Well-Defined Metallocarbenes and Metallocarbynes Supported on Oxide Supports Prepared via Surface Organometallic Chemistry: A Source of Highly Active Alkane, Alkene, and Alkyne Metathesis Catalysts
Christophe Copéret, Frédéric Lefebvre, and Jean-Marie Basset 		190
1.12.1 Introduction 190
1.12.2 Preparation and Characterization of Well-Defined Metallocarbenes and Metallocarbynes via Surface Organometallic Chemistry 191
1.12.2.1 Strategy and Tools in Surface Organometallic Chemistry 191
1.12.2.2 Application to the Preparation of Well-Defined Metallocarbene and Metallocarbyne Supported on Oxides 192
1.12.3 Reactivity in Alkene and Alkyne Metathesis 195
1.12.3.1 Group 5 and 6 Metallocarbenes and Metallocarbynes Supported on Oxides 195
1.12.3.2 Group 7 Metallocarbenes and Metallocarbynes Supported on Oxides 197
1.12.4 Reactivity in Alkane Metathesis 200
1.12.5 Summary and Outlook 201
  Acknowledgments 202
  References 202
  Index 205
  Volume 2  
  List of Contributors xxi
2.1 Olefin Metathesis and Related Reactions in Organic Synthesis: Introduction to Metal-Carbon Double Bonds in Organic Synthesis
Robert H. Grubbs 		1
  References 4
2.2 General Ring-Closing Metathesis
So-Yeop Han and Sukbok Chang 		5
2.2.1 Introduction 5
2.2.2 Synthesis of Carbocyles 7
2.2.2.1 Carbocyclization 7
2.2.2.2 Medium-Sized Carbocycles 16
2.2.2.3 Spiro Carbocycles 22
2.2.3 Synthesis of Bridged Bicycloalkenes 24
2.2.4 Synthesis of Heterocycles Containing Si, P, S, or B 29
2.2.4.1 Si-Heterocycles 29
2.2.4.2 P-Heterocycles 32
2.2.4.3 S-Heterocycles 35
2.2.4.4 B-Heterocycles 37
2.2.5 Synthesis of Cyclic Ethers 38
2.2.5.1 Mono- and Bicyclic Ethers 38
2.2.5.2 Polycyclic Ethers 43
2.2.6 Applications to N-Heterocycles and Peptide Chemistry 46
2.2.6.1 N-Heterocycles 46
2.2.6.2 Small and Medium-Sized Lactams 52
2.2.6.3 Cyclic Amino Acids, Peptides, and Peptidomimetics 54
2.2.7 Synthesis of Macrocycles 65
2.2.7.1 Macrocycles 66
2.2.7.2 Macrolactones 68
2.2.7.3 Macrolactams 73
2.2.8 Synthesis of Cyclic Conjugated Dienes 74
2.2.9 Alkyne Metathesis 77
2.2.10 Enyne Metathesis 80
2.2.10.1 General Enyne Metathesis 80
2.2.10.2 Dienyne Metathesis 83
2.2.11 Multi-Directional RCM 86
2.2.12 Tandem Processes 88
2.2.12.1 Tandem ROM/RCM 88
2.2.12.2 Other Tandem RCM 92
2.2.13 Asymmetric RCM 94
2.2.14 Synthesis of Complex Molecules 96
2.2.14.1 Template-Directed RCM 96
2.2.14.2 RCM in Supramolecular Chemistry 96
2.2.14.3 Synthetic Applications 109
  References 119
2.3 Catalytic Asymmetric Olefin Metathesis
Amir H. Hoveyda 		128
2.3.1 Introduction 128
2.3.2 The Catalyst Construct 129
2.3.3 Mo-Catalyzed Kinetic Resolution With Hexafluoro-Mo Catalysts 129
2.3.4 Chiral Mo-Diolate Complexes for Kinetic Resolution and Asymmetric Synthesis 130
2.3.4.1 Chiral Biphen-Mo Catalysts 130
2.3.4.2 Catalytic Kinetic Resolution Through Mo-Catalyzed ARCM 130
2.3.4.3 Catalyst Modularity and Optimization of Mo-Catalyzed ARCM Efficiency and Selectivity 131
2.3.4.4 Catalytic Asymmetric Synthesis Through Mo-Catalyzed ARCM 133
2.3.4.5 Catalytic Asymmetric Synthesis Through Tandem Mo-Catalyzed AROM/RCM 137
2.3.4.6 Catalytic Asymmetric Synthesis Through Tandem Mo-Catalyzed AROM/CM 142
2.3.4.7 Towards User-Friendly and Practical Chiral Mo-Based Catalysts for Olefin Metathesis 143
2.3.5 Chiral Ru-Based Olefin Metathesis Catalysts 145
2.3.6 Conclusions and Outlook 147
  Acknowledgments 148
  References 148
2.4 Tandem Ring-Closing Metathesis
Stefan Randl and Siegfried Blechert 		151
2.4.1 Introduction 151
2.4.2 Tandem Metathesis Involving Double Bonds Only 152
2.4.2.1 RRM of Alkenyl-Substituted Cycloolefins 152
2.4.2.2 RRM of bis Alkenyl-Substituted Cycloolefins 160
2.4.2.3 Tandem Reactions of Polycycloolefins 164
2.4.3 Tandem RCM Involving Enyne Reactions 164
2.4.3.1 Tandem Reactions with Triple Bonds As ``Relays'' 164
2.4.3.2 Tandem Processes Involving Ring Rearrangement 166
2.4.3.3 Alkyne Trimerizations Catalyzed by Metathesis Catalysts 169
2.4.3.4 Other Tandem Processes Involving C-C Triple Bonds 171
2.4.4 Summary and Outlook 172
  References 173
2.5 Ene-Yne Metathesis
Miwako Mori 		176
2.5.1 Introduction 176
2.5.2 Transition Metal-Carbene Complex-Catalyzed Enyne Metathesis 180
2.5.2.1 Ring-Closing Metathesis (RCM) of Enyne Using Ruthenium Carbene Complex 180
2.5.2.2 Ring-Opening Metathesis--Ring-Closing Metathesis of Cycloalkene-Yneo 186
2.5.2.3 Intermolecular Enyne Metathesis (Cross-Metathesis) 188
2.5.3 Skeletal Reorganization Using Transition Metals 194
2.5.4 Utilization of Enyne Metathesis for the Synthesis of Natural Products and Related Biologically Active Substances 198
2.5.5 Perspective 200
  References 203
2.6 Ring-Opening Cross-Metatheses
Thomas O. Schrader and Marc L. Snapper 		205
2.6.1 Introduction 205
2.6.2 Early Examples of ROCM 206
2.6.2.1 Mechanistic Insight 206
2.6.2.2 Early Efforts toward a Selective ROCM 207
2.6.2.3 Well-Defined Metal Complexes as Catalysts 209
2.6.2.4 New Opportunities for Olefin Metathesis 212
2.6.3 Selective ROCM Reactions 213
2.6.3.1 ROCM Involving Cyclobutenes 213
2.6.3.2 Regio- and Stereoselective ROCM 216
2.6.3.3 ROCM of Bridged Bicyclic Alkenes 218
2.6.3.4 ROCM Reactions of Cyclopropenes 223
2.6.3.5 ROCM Reactions Involving Unstrained Cycloolefins 224
2.6.3.6 ROCM Reactions of Trisubstituted Olefins 224
2.6.3.7 Variations of ROCM 226
2.6.3.8 Ring Expansion via Olefin Metathesis 226
2.6.4 Enantioselective ROCM 228
2.6.4.1 Mo-Catalyzed Asymmetric ROCM 228
2.6.4.2 A Recyclable Chiral Ruthenium Catalyst for Asymmetric ROCM 230
2.6.5 ROCM in Total Synthesis 230
2.6.6 Conclusions 233
  References 235
2.7 Ring-Expansion Metathesis Reactions
Choon Woo Lee 		238
  References 244
2.8 Olefin Cross-Metathesis
Arnab K. Chatterjee 		246
2.8.1 Olefin Forming Cross-Coupling Reactions 246
2.8.2 Olefin Metathesis and Selectivity Problems in CM 247
2.8.3 Metathesis Catalyst Overview 249
2.8.4 Selectivity Challenges in CM 250
2.8.5 Stereoselective CM Reactions 252
2.8.6 Product-Selective Reactions by CM 256
2.8.7 Styrene CM Reactions 258
2.8.8 Trisubstituted Olefin Synthesis by CM 261
2.8.9 Electron-Poor Olefins in CM 264
2.8.10 Reagent Synthesis by CM 269
2.8.11 Applications of CM 275
2.8.12 Bioorganic Applications of CM 278
2.8.13 CM Product-Selectivity Model 288
2.8.14 Conclusions 290
  References 292
2.9 Olefin Metathesis Strategies in the Synthesis of Biologically Relevant Molecules
Jennifer A. Love 		296
2.9.1 Introduction 296
2.9.1.1 Olefin Metathesis Strategies in Complex Molecule Synthesis 296
2.9.1.2 Catalysts for Olefin Metathesis 297
2.9.2 RCM and ROM in Complex Molecule Synthesis 298
2.9.2.1 Laulimalide 298
2.9.2.2 Boronolide 302
2.9.2.3 Ingenol 303
2.9.2.4 Asteriscanolide 303
2.9.2.5 (+)-FR900482 305
2.9.2.6 Salicylihalamide 306
2.9.2.7 Roseophilin 307
2.9.2.8 Ircinal A and Manzamine A 309
2.9.2.9 Amphidinolide A 309
2.9.2.10 Peptidomimetics 310
2.9.3 Ring-Closing Ene-Yne Metathesis 312
2.9.4 Cross-Metathesis in the Synthesis of Complex Molecules 314
2.9.4.1 (-)-Cylindrocyclophanes A and F 314
2.9.4.2 Garsubellin A 315
2.9.4.3 (+)-Brefeldin A 315
2.9.5 ROMP in Complex Molecule Synthesis 316
2.9.6 Conclusions 318
  References 319
2.9 Vignette 1
The Olefin Metathesis Reaction in Complex Molecule Construction
K. C. Nicolaou and Scott A. Snyder 		323
  Acknowledgments 334
  References 335
2.9 Vignette 2
Applications of Ring-Closing Metathesis to Alkaloid Synthesis
Stephen F. Martin 		338
  Introduction 338
  Methodological Studies 339
  Synthesis of Alkaloid Natural Products 342
  Conclusions 350
  Acknowledgments 351
  References 351
2.9 Vignette 3
Radicicol and the Epothilones: Total Synthesis of Novel Anticancer Agents Using Ring-Closing Metathesis
Jon T. Njardarson, Robert M. Garbaccio, and Samuel J. Danishefsky 		353
  References 359
2.10 The Use of Olefin Metathesis in Combinatorial Chemistry: Supported and Chromatography-Free Syntheses
Andrew M. Harned, Donald A. Probst, and Paul R. Hanson 		361
2.10.1 Introduction 361
2.10.2 Metathesis Reactions Toward Supported Synthesis and Library Generation 362
2.10.2.1 Ring-Closing Metathesis (RCM) 362
2.10.2.2 Cross-Metathesis (X-MET) 369
2.10.3 Polymer-Supported Metathesis Catalysts 375
2.10.4 ROMP-Based Strategies 377
2.10.4.1 ROMPgel Reagents 378
2.10.4.2 ROMP as a Purification Tool 386
2.10.4.3 ROMPspheres 390
2.10.4.4 ROM Polymers as Supports 391
2.10.5 Conclusions 396
  Acknowledgements 399
  References 399
2.11 Metal-Catalyzed Olefin Metathesis in Metal Coordination Spheres
Eike B. Bauer and J. A. Gladysz 		403
2.11.1 Introduction 403
2.11.2 Earliest Literature 404
2.11.3 Ferrocenes 405
2.11.4 Sophisticated Target Molecules: Catenanes and Knots 410
2.11.5 Systematic Investigation of Reaction Scope 414
2.11.6 Additional Literature Examples 420
2.11.7 Towards Additional Types of Sophisticated Target Molecules 425
2.11.8 Summary 429
2.11.9 Addendum 429
  Acknowledgments 429
  References 430
2.12 Alkyne Metathesis
Alois Fu¨rstner 		432
2.12.1 Introduction 432
2.12.2 Classical Catalyst Systems for Alkyne Metathesis 432
2.12.3 Recent Advances in Catalyst Design 434
2.12.4 Preparative Applications of Alkyne Metathesis 437
2.12.4.1 Alkyne Homometathesis Reactions 437
2.12.4.2 Alkyne Cross-Metathesis 439
2.12.4.3 Ring-Closing Alkyne Metathesis (RCAM) 443
2.12.4.4 Applications of RCAM to Natural Product Synthesis 448
2.12.4.5 Post-Metathesis Transformations Other Than Lindlar Hydrogenation: Selective Synthesis of (E)-Alkenes and Heterocyclic Motifs 456
2.12.5 Conclusions and Outlook 458
  References 459
2.13 Metathesis of Silicon-Containing Olefins
Bogdan Marciniec and Cezary Pietraszuk 		463
2.13.1 Introduction 463
2.13.2 Self-Metathesis of Alkenylsilanes 464
2.13.3 Cross-Metathesis vs. Silylative Coupling (Trans-Silylation) of Alkenes with Vinylsilanes 464
2.13.4 Cross-Metathesis of Allylsilanes with Alkenes 470
2.13.5 Ring-Closing Metathesis of Silicon-Containing Dienes 472
2.13.6 Ring-Opening Metathesis/Cross-Metathesis 476
2.13.7 Polycondensation vs. Ring Closing of Divinyl-Substituted Silicon Compounds 478
2.13.8 ADMET Polymerization of Silicon-Containing Dienes 481
2.13.9 Ring-Opening Metathesis Polymerization of Silacycloalkenes 483
2.13.10 Ring-Opening Metathesis Polymerization of Silyl-Substituted Cycloalkenes 483
2.13.11 Degradation vs. Functionalization of Polymers 485
  References 486
2.14 Commercial Applications of Ruthenium Metathesis Processes
Richard L. Pederson 		491
2.14.1 Introduction 491
2.14.2 Fine Chemicals 491
2.14.2.1 Agrochemicals: Insect Pheromones 492
2.14.2.2 Polymer Additives 494
2.14.2.3 Fuel Additives 494
2.14.2.4 Drug Discovery 494
2.14.3 Pharmaceutical Applications 495
2.14.4 Future Directions for Metathesis 505
2.14.5 Summary 506
  References 507
  Index 511
  Volume 3  
  List of Contributors xxi
3.1 Introduction
Robert H. Grubbs 		1
3.2 Living Ring-Opening Olefin Metathesis Polymerization
Gráinne Black, Declan Maher, and Wilhelm Risse 		2
3.2.1 Historic Overview of Living Polymerization Systems 2
3.2.2 Definition of Living Polymerization and Relevant Terminology 4
3.2.3 Introduction to ROMP 6
3.2.4 Olefin Metathesis Catalysts for Living Polymerizations 11
3.2.4.1 Titanacyclobutane Compounds 11
3.2.4.2 Tantalum-Alkylidene and Tantalacyclobutane Complexes for Norbornene Polymerizations 16
3.2.4.3 Tungsten Catalysts 17
3.2.4.4 Imido Molybdenum-Alkylidene Complexes 21
3.2.4.5 Imido Tungsten- and Molybdenum-Alkylidene Catalysts for ROMP of Monomers Containing Cyclobutene, Bicyclooctadiene, and Bicyclooctatriene Ring Systems 33
3.2.4.6 Tungsten- and Molybdenum-Alkylidene Catalysts in Cyclopentene Polymerizations 42
3.2.4.7 Paracyclophene Polymerizations 43
3.2.4.8 Ruthenium Catalysts and Living ROMP 44
3.2.4.9 Star-Shaped Polymers via ROMP 63
  References 66
3.3 Synthesis of Copolymers
Ezat Khosravi 		72
3.3.1 Introduction 72
3.3.2 Random Copolymers 72
3.3.3 Block Copolymers 76
3.3.3.1 Sequential Addition of Monomers 76
3.3.3.2 Coupling Reaction 83
3.3.3.3 Transformation of Propagating Species 84
3.3.3.4 Application of Well-Defined Bimetallic Initiators 90
3.3.4 Comb and Graft Copolymer 92
3.3.4.1 Combination of ROMP and Anionic Polymerization 92
3.3.4.2 Combination of ROMP and ATRP 94
3.3.4.3 Combination of ROMP and Cationic Polymerization 95
3.3.4.4 Combination of ROMP and Wittig-Type Reaction 96
3.3.4.5 Repetitive ROMP 96
3.3.5 Multi-Shaped Copolymers 98
3.3.6 Alternating Copolymers 103
3.3.7 Cross-Linked Copolymers 105
3.3.7.1 Well-Defined, Cross-Linked System via Direct Copolymerization 105
3.3.7.2 Cross-Linked Systems via Homopolymerization of Monomers with Cross-Linkable Side Chains 110
3.3.7.3 Cross-Linked Material via Combination of ROMP and Oxidative Polymerization 112
  References 113
3.4 Conjugated Polymers
W. James Feast 		118
3.4.1 Introduction 118
3.4.2 Strategies for Applying ROMP in the Synthesis of Conjugated Polymers 121
3.4.3 Direct Routes from Monomer to Conjugated Polymer Via Chain-Growth Processes 122
3.4.4 Direct Routes from Monomer to Conjugated Polymer Via Step-Growth Processes 127
3.4.5 Indirect Routes to Conjugated Polymer Via Processable Precursor Polymers 129
3.4.6 Conclusions 139
  References 139
3.5 Stereochemistry of Ring-Opening Metathesis Polymerization
James G. Hamilton 		143
3.5.1 Introduction 143
3.5.2 Consequences of cis/trans Isomerism and Tacticity in ROMP Polymers 144
3.5.3 Determination of the Stereochemistry of ROMP Polymers 146
3.5.3.1 Cis/trans Double-Bond Ratio 146
3.5.3.2 Tacticity 149
3.5.4 Control and Interpretation of Stereochemistry 156
3.5.4.1 Ratio and Distribution of cis and trans Double Bonds 156
3.5.4.2 Tacticity 169
  References 176
3.6 Syntheses and Applications of Bioactive Polymers Generated by Ring-Opening Metathesis Polymerization
Laura L. Kiessling and Robert M. Owen 		180
3.6.1 Introduction 180
3.6.2 Synthesis of Biologically Active Polymeric Displays 183
3.6.2.1 Carbohydrate-Containing Polymeric Displays 183
3.6.2.2 Peptide-Substituted Polymers 189
3.6.2.3 Synthesis of DNA/Polymer Conjugates via ROMP 193
3.6.2.4 Synthesis of Drug/Polymer Conjugates via ROMP 195
3.6.2.5 Post-Polymerization Modification Strategies 196
3.6.2.6 End-Capping Strategies 199
3.6.3 Applications of Biologically Active Polymeric Displays 203
3.6.3.1 Protein-Carbohydrate Interactions 203
3.6.3.2 Integrins and Cellular Adhesion 211
3.6.3.3 Pathogenic Organisms 213
3.6.3.4 Cell Clustering 216
3.6.3.5 Bacterial Chemotaxis 216
3.6.4 Conclusions 220
  References 222
3.7 Metathesis Polymerization: A Versatile Tool for the Synthesis of Surface-Functionalized Supports and Monolithic Materials
Michael R. Buchmeiser 		226
3.7.1 Introduction 226
3.7.2 Precipitation Polymerization-Based Techniques 226
3.7.3 Grafting Techniques 230
3.7.4 Coating Techniques 239
3.7.5 Monolithic Supports 240
3.7.5.1 Basics and Concepts 241
3.7.5.2 Manufacture of Metathesis-Based Monolithic Supports 242
3.7.5.3 Microstructure of Metathesis-Based Rigid Rods 242
3.7.5.4 Functionalization, Metal Removal, and Metal Content 245
3.7.5.5 Applications of Functionalized Metathesis-Based Monoliths in Catalysis 247
3.7.6 Conclusions, Summary, and Outlook 251
  Acknowledgments 251
  References 251
3.8 Telechelic Polymers from Olefin Metathesis Methodologies
Christopher W. Bielawski and Marc A. Hillmyer 		255
3.8.1 Introduction and Background 255
3.8.2 Telechelic Polymers from Metathesis Polymerizations 258
3.8.2.1 Molecular Weight and Functionality Control in a ROMP/CT System 260
3.8.3 Syntheses and Applications of Telechelic Polymers Prepared Using Metathesis 263
3.8.3.1 Synthesis of Telechelic Polymers Using Ill-Defined Catalysts 264
3.8.3.2 Synthesis of Telechelic Polymers Using Well-Defined Metal Alkylidenes 267
3.8.3.3 Synthesis of End-Functionalized Polymers Using Functionalized Initiators 277
3.8.4 Conclusions and Outlook 279
  References 280
3.9 ADMET Polymerization
Stephen E. Lehman, Jr. and Kenneth B. Wagener 		283
3.9.1 Introduction 283
3.9.2 ADMET: The Metathesis Polycondensation Reaction 288
3.9.2.1 Kinetics and Equilibrium Considerations 289
3.9.2.2 Molecular Weight Distribution 291
3.9.2.3 Interchange Reactions 291
3.9.2.4 Cyclization vs. Polymerization 292
3.9.2.5 Monomer Purity 293
3.9.3 Early Observations in the Evolution of ADMET Polymerization: Reactions of Non-Conjugated Dienes with Classical Metathesis Catalysts 294
3.9.4 ADMET of Non-Conjugated Hydrocarbon Dienes with Well-Defined Metathesis Catalysts 297
3.9.4.1 Linear Terminal Dienes 297
3.9.4.2 Branched Terminal Dienes 300
3.9.4.3 Geminal Disubstituted Olefins 305
3.9.4.4 1,2-Disubstituted Olefins 307
3.9.4.5 Trisubstituted Olefins 308
3.9.5 ADMET Copolymerization 310
3.9.6 Synthesis of Conjugated Polymers via ADMET 311
3.9.6.1 Polyacetylenes 311
3.9.6.2 Polyphenylenevinylenes 313
3.9.6.3 Other Conjugated Polymers 315
3.9.7 ADMET Polymerization of Functionalized Dienes 316
3.9.7.1 Ethers, Acetals, and Alcohols 318
3.9.7.2 Amines 319
3.9.7.3 Boronates 320
3.9.7.4 Thioethers 321
3.9.7.5 Carbonyl Compounds 322
3.9.7.6 Halides 325
3.9.7.7 Silicon Compounds 325
3.9.7.8 Organometallic Compounds 329
3.9.8 Retro-ADMET: Towards Recycling of Unsaturated Polymers with Well-Defined Metathesis Catalysts 329
3.9.9 Telechelic Oligomers via ADMET 331
3.9.10 Kinetics and Mechanism 332
3.9.11 Modeling Polyolefins with ADMET 338
3.9.11.1 Hydrogenation of ADMET Polymers 338
3.9.11.2 Branched Polyethylene 339
3.9.11.3 Functionalized Polyethylene 342
3.9.12 Towards Biologically Useful Polymers via ADMET 345
3.9.13 Solid-State Polymerization 347
3.9.14 Conclusions and Outlook 347
  References 347
3.10 Acyclic Diyne Metathesis Utilizing in Situ Transition Metal Catalysts: An Efficient Access to Alkyne-Bridged Polymers
Uwe H. F. Bunz 		354
3.10.1 Introduction 354
3.10.1.1 Alkyne Metathesis 355
3.10.2 ADIMET: Synthesis of Alkyne-Bridged Polymers 357
3.10.2.1 Synthesis of PPEs by in situ ADIMET 360
3.10.2.2 Synthesis of PPE-PPV Copolymers by in situ ADIMET 363
3.10.2.3 Synthesis of Other PAEs by ADIMET 365
3.10.2.4 Alkyne-Bridged Carbazole Polymers (PCE) by ADIMET 370
3.10.3 Conclusions 370
  Acknowledgments 371
  References 371
3.11 Polymerization of Substituted Acetylenes
Toshio Masuda and Fumio Sanda 		375
3.11.1 Introduction 375
3.11.2 Polymerization Catalysts 378
3.11.2.1 Mo and W Catalysts 378
3.11.2.2 Nb and Ta Catalysts 381
3.11.2.3 Rh Catalysts 382
3.11.2.4 Other Group 8--10 Metal Catalysts 384
3.11.3 Controlled Polymerizations 384
3.11.3.1 Living Polymerization by Metal Halide-Based Metathesis Catalysts 385
3.11.3.2 Living Polymerization by Single-Component Metal-Carbene Catalysts 387
3.11.3.3 Stereospecific Living Polymerization by Rh Catalysts 388
3.11.4 New Monomers and Functional Polymers 389
3.11.4.1 Gas-Permeable Polyacetylenes 396
3.11.4.2 Optically Active Polyacetylenes 397
3.11.4.3 Other Functional Polyacetylenes 399
  References 401
3.12 Commercial Applications of Ruthenium Olefin Metathesis Catalysts in Polymer Synthesis
Mark S. Trimmer 		407
3.12.1 Introduction 407
3.12.2 Background 407
3.12.3 New Developments 408
3.12.4 Poly-DCPD 409
3.12.5 Other ROMP Polymers 411
3.12.6 Hydrogenated ROMP Polymers 413
3.12.7 Depolymerization 414
3.12.8 Summary 414
  References 414
  Index 419

 
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