Note: Intro -- Metathesis in Natural Product Synthesis: Strategies, Substrates and Catalysts -- Contents -- Foreword -- Preface -- List of Catalysts -- List of Contributors -- Abbreviations -- 1 Synthesis of Natural Products Containing Medium-size Carbocycles by Ring-closing Alkene Metathesis -- 1.1 Introduction -- 1.2 Formation of Five-membered Carbocycles by RCM -- 1.3 Formation of Six-membered Carbocycles by RCM -- 1.4 Formation of Seven-membered Carbocycles by RCM -- 1.5 Formation of Eight-membered Carbocycles by RCM -- 1.6 Formation of Nine-membered Carbocycles by RCM -- 1.7 Formation of 10-membered Carbocycles by RCM -- 1.8 Conclusion -- References -- 2 Natural Products Containing Medium-sized Nitrogen Heterocycles Synthesized by Ring-closing Alkene Metathesis -- 2.1 Introduction -- 2.2 Five-membered Nitrogen Heterocycles -- 2.2.1 Dihydropyrroles -- 2.2.2 Pyrrolidine Alkaloids -- 2.2.2.1 Pyrrolidines -- 2.2.2.2 Dipyrrolidines -- 2.2.2.3 Polyhydroxypyrrolidines -- 2.2.3 Indolizidine Alkaloids -- 2.2.3.1 Polycyclic Indolizidines -- 2.2.3.2 Polyhydroxyindolizidines -- 2.2.4 Pyrrolizidine Alkaloids -- 2.3 Six-membered Nitrogen Heterocycles -- 2.3.1 Piperidine Alkaloids -- 2.3.1.1 Piperidines -- 2.3.1.2 Piperidine Carboxylic Acids -- 2.3.1.3 Piperidones -- 2.3.1.4 Polyhydroxypiperidines -- 2.3.2 Indolizidine Alkaloids -- 2.3.3 Quinolizidine Alkaloids -- 2.4 Seven-membered Nitrogen Heterocycles -- 2.5 Eight-membered Nitrogen Heterocycles -- 2.6 Conclusion -- References -- 3 Synthesis of Natural Products Containing Medium-size Oxygen Heterocycles by Ring-closing Alkene Metathesis -- 3.1 Introduction -- 3.2 General RCM Approaches to Medium Rings -- 3.3 Laurencin -- 3.4 Eunicellins/Eleutherobin -- 3.5 Helianane -- 3.6 Octalactin A -- 3.7 Microcarpalide and the Herbarums -- 3.8 Marine Ladder Toxins -- 3.8.1 Ciguatoxin -- 3.8.2 Brevetoxin. , 3.8.3 Gambierol, Gambieric Acid, Olefinic-ester Cyclizations -- 3.9 Conclusion -- Acknowledgments -- References -- 4 Phosphorus and Sulfur Heterocycles via Ring-closing Metathesis: Application in Natural Product Synthesis -- 4.1 Introduction -- 4.2 Synthesis and Reactivity of Sultones Derived from RCM -- 4.3 Total Synthesis of the Originally Proposed Structure of (±)-Mycothiazole -- 4.4 Synthesis and Reactivity of Phosphates from RCM -- 4.5 Applications of Phosphate Tethers in the Synthesis of Dolabelide C -- 4.6 Conclusion -- Acknowledgment -- References -- 5 Synthesis of Natural Products Containing Macrocycles by Alkene Ring-closing Metathesis -- 5.1 Introduction -- 5.2 Organization of the Chapter -- 5.3 Macrocyclic Polyketides -- 5.3.1 Resorcinylic Macrolides -- 5.3.2 Salicylate Macrolides -- 5.3.3 Other Antibiotic Macrolides -- 5.3.4 Macrocyclic Musk -- 5.3.5 Epothilones -- 5.3.6 Amphidinolides -- 5.3.7 Other Polyketides -- 5.3.8 Natural Cyclophanes -- 5.4 Terpenoids -- 5.4.1 Diterpenoids -- 5.4.2 Macrocyclic Lipids -- 5.5 Macrocycles of Amino Acid Origin -- 5.5.1 Macrolactams -- 5.5.2 Cyclodepsipeptides -- 5.5.3 Alkaloids -- 5.6 Macrocyclic Glycolipids -- 5.7 Conclusions and Outlook -- References -- 6 Synthesis of Natural Products and Related Compounds Using Ene-Yne Metathesis -- 6.1 Introduction -- 6.2 Synthesis of Natural Products and Related Compounds Using Ene-yne Metathesis -- 6.3 Synthesis of Natural Products and Related Compounds Using Ene-yne Cross-metathesis (CM) -- 6.4 Synthesis of Natural Products Using Skeletal Reorganization -- References -- 7 Ring-closing Alkyne Metathesis in Natural Product Synthesis -- 7.1 Introduction -- 7.2 Alkyne Metathesis -- 7.2.1 Background to Alkyne Metathesis -- 7.3 Ring-closing Alkyne Metathesis -- 7.3.1 RCAM as a Synthetic Strategy -- 7.4 Applications of RCAM in Natural Product Synthesis. , 7.4.1 RCAM/Hydrogenation Strategies -- 7.4.1.1 Macrocyclic Musks -- 7.4.1.2 Prostaglandin Lactones -- 7.4.1.3 Sophorolipid Lactone -- 7.4.1.4 Epothilone A -- 7.4.1.5 Cruentaren A -- 7.4.1.6 Latrunculins A, B, C, M, and S -- 7.4.1.7 Myxovirescin A1 -- 7.4.2 RCAM and Alternative Alkyne Manipulations -- 7.4.2.1 Citreofuran -- 7.4.2.2 Amphidinolide V -- 7.5 Conclusions -- References -- 8 Temporary Silicon-Tethered Ring-Closing Metathesis Reactions in Natural Product Synthesis -- 8.1 Introduction -- 8.2 Temporary Silicon-Tethered Ring-Closing Metathesis Reactions -- 8.2.1 O-SiR2 -O Tethered Substrates: Symmetrical Silaketals -- 8.2.1.1 C2-Symmetrical Silaketals and Applications -- 8.2.1.2 Achiral and Racemic Silaketals -- 8.2.1.3 Related Applications and Developments -- 8.2.2 O-SiR2 -O Tethered Substrates: Unsymmetrical Silaketals -- 8.2.2.1 Spiroketals -- 8.2.2.2 Long-range Asymmetric Induction -- 8.2.2.3 Annonaceous Acetogenins -- 8.2.2.4 Trisubstituted Alkenes -- 8.2.2.5 Related Applications and Developments -- 8.2.3 Dienyne TST-RCM: Symmetrical and Unsymmetrical Silanes -- 8.2.3.1 Macrolide Antibiotics -- 8.2.4 O-SiR2 -C Tethered Substrates: Allyl and Vinylsiloxanes -- 8.2.4.1 Lignans from Allylsiloxanes -- 8.2.4.2 Z-Trisubstituted Alkenes from Allylsiloxanes -- 8.2.4.3 Di- and Trisubstituted Alkenes from Vinylsiloxanes -- 8.2.4.4 Related Applications and Developments -- 8.2.5 Enyne TST-RCM: Tri- and Tetrasubstituted Acyclic Dienes -- 8.2.5.1 Illudins -- 8.3 Conclusions and Outlook -- Acknowledgments -- References -- 9 Metathesis Involving a Relay and Applications in Natural Product Synthesis -- 9.1 Introduction -- 9.1.1 The Relay Concept -- 9.1.2 Basic Tenets of RCM -- 9.2 Early Relay Metathesis Discoveries -- 9.3 Examples of Relay Metathesis Directed at Targets Other than Natural Products. , 9.4 Examples of Relay Metathesis Motivated by Natural Product Synthesis -- 9.5 Examples of Relay Metatheses Thwarted in Achieving the Desired Outcome -- 9.5.1 Interference from a Truncation Event -- 9.5.2 Interference from Premature Macrocyclization -- 9.6 Conclusion -- Acknowledgments -- References -- 10 Cross-metathesis in Natural Products Synthesis -- 10.1 Introduction -- 10.2 Functionalization of Olefins -- 10.2.1 Cross-metathesis with Acrylate Derivatives -- 10.2.1.1 Acrylonitrile -- 10.2.1.2 Thioacrylates -- 10.2.1.3 Acrylic Acid -- 10.2.1.4 Acrylimides -- 10.2.1.5 Acrylates -- 10.2.1.6 Acrolein -- 10.2.1.7 Vinyl Ketones -- 10.2.2 Cross-metathesis with Vinyl Derivatives -- 10.2.2.1 Vinyl Boronates -- 10.2.2.2 Vinyl Silanes -- 10.2.3 Cross-metathesis with Allylic Derivatives -- 10.2.3.1 Allyl Silanes -- 10.2.3.2 Allyl Phosphonates -- 10.2.3.3 Allylic Alcohol Derivatives -- 10.2.3.4 Miscellaneous -- 10.3 Appending a Side Chain -- 10.3.1 With No Functional Group -- 10.3.1.1 A Simple Case -- 10.3.1.2 The Specific Case of Isopropylidene -- 10.3.1.3 Removing Part of a Side Chain -- 10.3.2 With Functional Groups -- 10.4 Couplings -- 10.5 Cascade Processes Involving CM -- 10.5.1 ROM/CM -- 10.5.2 ROM/CM/RCM -- 10.5.3 ROM/RCM/CM -- 10.5.4 CM/RCM -- 10.5.5 RCEYM/CM -- 10.6 Ene-yne CM -- 10.7 Alkyne CM -- 10.8 Conclusion and Perspectives -- Acknowledgments -- References -- 11 Cascade Metathesis in Natural Product Synthesis -- 11.1 Introduction -- 11.2 RCM-CM Sequences -- 11.2.1 Ene-ene RCM-CM -- 11.2.1.1 Synthesis of (3R,9R,10R)-Panaxytriol -- 11.2.2 Ene-yne-ene RCM-CM -- 11.2.2.1 Synthesis of (+)-8-epi-Xanthatin -- 11.3 Ene-yne-ene RCM-RCM -- 11.3.1 Synthesis of Bicyclic Structures -- 11.3.1.1 Synthesis of (-)-Securinine and (+)-Viroallosecurinine -- 11.3.1.2 Total Synthesis of ent-Lepadin F and G -- 11.3.2 Synthesis of Tricyclic Compounds. , 11.3.2.1 Synthesis of (±)-Guanacastepene A -- 11.3.2.2 Approach to Taxane Analogs -- 11.3.3 Synthesis of Natural Products Containing Tetracycles -- 11.3.3.1 Synthesis of Erythrina Alkaloids -- 11.4 ROM-CM Sequences -- 11.4.1 Synthesis of Bistramide A -- 11.5 RCM-ROM Sequences - Ring-rearrangement Metathesis (RRM) -- 11.5.1 RRM of Monocyclic Substrates -- 11.5.1.1 Synthesis of Tetraponerines -- 11.5.1.2 Synthesis of (-)-Swainsonine and (+)-Castanospermine -- 11.5.1.3 Synthesis of (+)-trans-195A -- 11.5.1.4 Synthesis of (-)-Centrolobine - Diastereoselective RRM (d-RRM) -- 11.5.2 RRM of Bicyclic Substrates -- 11.5.2.1 Synthesis of Indolizidine 251F, (±)-trans-Lumausyne and Aburatubolactam A -- 11.5.2.2 Synthesis of (+)-ent-Lepadin B -- 11.6 RCM-ROM Sequences Combined with Other Metathesis Reactions -- 11.6.1 RCM-ROM-RCM -- 11.6.1.1 RCM-ROM-RCM Cascades of Monocyclic Structures -- 11.6.1.2 RCM-ROM-RCM Cascades of Bicyclic Structures -- 11.6.2 RCM-ROM-CM -- 11.6.2.1 Synthesis of (-)-Lasubine II -- 11.6.2.2 Synthesis of (+)-Cylindramide A and Bicyclic Core of Geodin A -- 11.6.2.3 Total Synthesis of (+)-Mycoepoxydiene -- 11.7 Conclusions and Outlook -- References -- 12 Catalytic Enantioselective Olefin Metathesis and Natural Product Synthesis -- 12.1 Introduction -- 12.2 Total Synthesis of Natural Products with Enantiomerically Pure Chiral Olefin Metathesis Catalysts Bearing a C2-symmetric Diolate Ligand -- 12.2.1 Total Synthesis of Coniine through Enantioselective RCM with Substrates Bearing a Tertiary Amine -- 12.2.2 Enantioselective Synthesis of Africanol by a Ring-opening/Ring-closing Metathesis Reaction -- 12.2.3 Enantioselective Synthesis of the Lactone Fragment of Anti-HIV Agent Tipranivir -- 12.3 Enantioselective Synthesis of Quebrachamine through an Exceptionally Challenging RCM Reaction. , 12.4 Synthesis of Baconipyrone C by Ru-catalyzed Enantioselective ROCM.

Note: Cover -- Title Page -- Copyright -- Contents -- Foreword -- Preface -- Chapter 1 Industrial Milestones in Organometallic Chemistry -- 1.1 Definition of Organometallic and Metal-Organic Compounds -- 1.1.1 Applications and Key Reactivity -- 1.1.1.1 Electronic Applications -- 1.1.1.2 Polymers -- 1.1.1.3 Organic Synthesis -- 1.2 Industrial Process Considerations -- 1.3 Brief Notes on the Historical Development of Organometallic Chemistry for Organic Synthesis Applications Pertaining to the Contents of this Book -- 1.3.1 Synthesis of Stoichiometric Organometallic Reagents -- 1.3.1.1 Conventional Batch Synthesis -- 1.3.1.2 Organometallics in Flow -- 1.3.2 Cross‐coupling Reactions -- 1.3.2.1 C-HBond Activation -- 1.3.2.2 Carbonylation -- 1.3.2.3 Catalysis in Water - Micellar Catalysis -- 1.3.3 Hydrogenation Reactions -- 1.3.4 Olefin Formation Reactions -- 1.3.4.1 Wittig Reaction -- 1.3.4.2 Metathesis Reactions -- 1.3.4.3 Dehydrative Decarbonylation -- 1.3.4.4 Olefins as Starting Materials -- 1.3.5 Poly‐ or Oligomerization Processes -- 1.3.6 Photoredox Catalysis for Organic Synthesis -- 1.4 Conclusion and Outlook -- Biography -- References -- Chapter 2 Design, Development, and Execution of a Continuous‐flow‐Enabled API Manufacturing Route -- 2.1 Continuous‐flow‐Enabled Synthetic Strategy -- 2.2 Design and Scale‐up of Chan-Lam Coupling -- 2.2.1 Development of Homogeneous Conditions -- 2.2.2 Application of a Platform Technology to Aerobic Oxidation -- 2.2.3 Optimization of Reaction and Workup Parameters -- 2.2.4 Safety Considerations for Aerobic Oxidation on Scale -- 2.2.5 Continuous Scale‐up and Manufacturing -- 2.3 Design and Scale‐up of a Buchwald-Hartwig Cross‐coupling -- 2.3.1 Initial Screening -- 2.3.2 Synthesis and Isolation of Pd(dba)DPEPhos Precatalyst -- 2.3.3 Workup Procedure, Metal Removal, and Crystallization. , 2.3.4 Scale‐up and Manufacturing -- 2.4 Impurity Control -- 2.4.1 Solubility and Impurity Spiking Studies -- 2.5 Conclusions -- Biography -- References -- Chapter 3 Continuous Manufacturing as an Enabling Technology for Low‐Temperature Organometallic Chemistry -- 3.1 Introduction -- 3.2 Organo‐Li and Mg Processes in Flow Mode -- 3.2.1 Technological Advantages of Flow Technology Compared to Traditional Batch Operation -- 3.2.2 Temperature Profile of Continuous Flow Reactions -- 3.2.3 Flash Chemistry: Functional Group Tolerance -- 3.2.4 Flash Chemistry: Selectivity -- 3.2.5 Flash Chemistry: Stoichiometry and Chemoselectivity -- 3.3 Continuous Flow Technology -- 3.3.1 Clogging as a Major Hurdle in Flow Chemistry -- 3.3.2 Start‐up and Shutdown Operation -- 3.3.3 Material of Construction -- 3.3.4 Safety Concept and Emergency Strategies -- 3.4 Development of a Flow Process -- 3.4.1 Screening Phase: Feasibility Study -- 3.4.2 Process Development Phase: Extended Evaluations Including Technical Feasibility -- 3.5 Literature Examples: Flow Processes on Multi 100 g Scale -- 3.5.1 Manufacture of Verubecestat (MK‐8931) -- 3.5.2 Manufacture of Edivoxetine -- 3.5.3 Scale‐up of Highly Reactive Aryl Lithium Chemistry -- 3.5.4 Synthesis of Bromomethyltrifluoroborates in Continuous Flow Mode -- 3.5.5 Two‐Step Synthesis Toward Boronic Acids -- 3.5.6 Reaction Sequence Toward a Highly Substituted Benzoxazole Building Block -- 3.6 Conclusion and Future Prospects -- Biography -- References -- Chapter 4 Development of a Nickel‐Catalyzed Enantioselective Mizoroki-Heck Coupling -- 4.1 Introduction -- 4.1.1 Nonprecious Metal Catalysis Advantages for Industry -- 4.1.2 Mizoroki-Heck Couplings in Industry with Palladium -- 4.1.3 Emergence of Nickel‐Catalyzed Mizoroki-Heck Couplings -- 4.1.4 Enantioselective Nickel‐Catalyzed Couplings. , 4.1.5 Synthesis of Oxindoles via Mizoroki-Heck Cyclizations -- 4.2 Development of a Nickel‐Catalyzed Heck Cyclization to Generate Oxindoles with Quaternary Stereogenic Centers -- 4.2.1 Precedents and Challenges -- 4.2.2 Optimization of Reducing Agent and Base -- 4.2.3 Ligand Screening -- 4.2.4 Impact of Aryl Electrophile and of Stereochemistry of Alkene Moiety -- 4.2.5 Exploration of the Substrate Scope -- 4.2.6 Limitations of the Methodology -- 4.2.7 Mechanistic Considerations -- 4.3 Development of First Enantioselective Nickel‐Catalyzed Heck Coupling -- 4.3.1 Ligand Screening -- 4.3.2 Impact of Alkene Stereochemistry -- 4.3.3 Neutral vs Cationic Pathways -- 4.3.4 Nickel Precatalyst Complex Synthesis -- 4.3.5 Exploration of the Substrate Scope -- 4.3.6 Mechanistic Studies -- 4.4 Conclusions -- Biography -- References -- Chapter 5 Development of Iron‐Catalyzed Kumada Cross‐coupling for the Large‐Scale Production of Aliskiren Intermediate -- 5.1 Introduction -- 5.2 Optimization of Grade and Equivalents of Mg Metal -- 5.3 Optimization of Equivalents of 1,2‐Dibromoethane -- 5.4 Effect of Solvent Concentration on Preparation of Grignard Reagent and Kumada-Corriu Coupling -- 5.5 Effect of Alkyl Chloride 3 Addition Time on the Grignard Reagent Preparation -- 5.6 Stability of Grignard Reagent at 0-5 °C -- 5.7 Iron‐Catalyzed Cross‐coupling Reaction -- 5.8 Optimization of Equivalents of NMP and Fe(acac)3 -- 5.9 Optimization of Equivalents of Substrate 4 and Its Rate of Addition -- 5.10 Execution at Pilot Scale and Scale‐up Issues -- 5.11 Agitated Thin Film Evaporator (ATFE) for Purification of 2 -- 5.12 Conclusion -- Acknowledgments -- Biography -- References -- Chapter 6 Development and Scale‐Up of a Palladium‐Catalyzed Intramolecular Direct Arylation in the Commercial Synthesis of Beclabuvir -- 6.1 Introduction -- 6.2 KOAc/DMAc Process. , 6.3 TMAOAc/DMF Process -- 6.4 TMAOAc/DMAc Process -- 6.4.1 Cyclization Reaction -- 6.4.2 Mechanistic Understanding of the Cyclization Reaction and Impurity Formation -- 6.4.3 Hydrolysis and Workup -- 6.4.4 Crystallization and Drying -- 6.5 Conclusion -- Biography -- References -- Chapter 7 Ruthenium‐Catalyzed C-H Activated C-C/N/O Bond Formation Reactions for the Practical Synthesis of Heterocycles and Pharmaceutical Agents -- 7.1 Introduction -- 7.2 C-H Activation Followed by C C Bond Formation -- 7.2.1 C-H Activation Followed by C C Bond Formation: Biaryl/Heterobiaryl Synthesis in Organic Solvents -- 7.2.2 C-H Activation Followed by C C Bond Formation: Biaryl/Heterobiaryl Synthesis in Green Solvents -- 7.3 Alkyl/Acyl/Alkenyl Substitution on Heterocycles -- 7.4 C-H Activation Followed by C O/N Bond Formation: Heterocycle Synthesis -- 7.4.1 C-H Activation Followed by C O/N Bond Formation: Heterocycle Synthesis in Organic Solvents -- 7.4.2 C-H Activation Followed by C O and C N Bond Formation: Heterocycle Synthesis in Green Solvents -- 7.5 Conclusion -- Biography -- References -- Chapter 8 Cross‐couplings in Water - A Better Way to Assemble New Bonds -- 8.1 Introduction -- 8.2 Transition Metal Catalysis in Organic Solvents vs Micellar Catalysis -- 8.2.1 Micellization -- 8.2.2 Surfactant Solution - A Highly Organized Reaction Medium to Enhance Reaction Rate -- 8.2.3 Reaction Temperature -- 8.2.4 Size of Micelles -- 8.2.5 Nature of Catalyst -- 8.2.6 Increasing the Efficiency in Micellar Catalysis -- 8.2.7 Order of Addition -- 8.2.8 Product Precipitation or Extraction -- 8.2.9 Trace Metal in the Product -- 8.3 Highly Valuable Reactions in Water -- 8.3.1 Suzuki-Miyaura Couplings -- 8.3.2 Heck Couplings -- 8.3.3 Negishi Couplings -- 8.3.4 C-H Arylations -- 8.3.5 Aminations -- 8.3.6 Borylation -- 8.3.7 Arylation of Nitro Compounds. , 8.3.8 Adoption of Micellar Technology by Pharmaceutical Industry -- 8.4 Conclusions -- Biography -- References -- Chapter 9 Aspects of Homogeneous Hydrogenation from Industrial Research -- 9.1 Homogeneous Hydrogenation: A Brief Introduction -- 9.2 Catalyst Selection by Effective Screening Approaches -- 9.3 Considerations for Reaction Scale‐up -- 9.4 Notes on Additive Effects -- 9.5 A Novel Approach to Aliskiren Using Asymmetric Hydrogenation as a Key Step -- 9.6 Efficient Chemoselective Aldehyde Hydrogenation -- 9.7 Closing Remarks/Summary -- Biography -- References -- Chapter 10 Latest Industrial Uses of Olefin Metathesis -- 10.1 Introduction -- 10.2 General Information -- 10.2.1 Non‐ruthenium Catalysts -- 10.2.2 Ruthenium Catalysts -- 10.3 Industrial Uses -- 10.3.1 Ring‐closing Metathesis (RCM) -- 10.3.2 Cross‐metathesis (CM) -- 10.3.3 Ring‐Opening Metathesis Polymerization (ROMP) -- 10.4 Reaction Considerations -- 10.4.1 Catalyst Choice -- 10.4.2 Catalyst Loading -- 10.4.3 Solvent -- 10.4.4 Reaction Concentration -- 10.4.5 Overall Handling -- 10.4.6 Application Guide and Availability -- 10.5 Troubleshooting -- 10.5.1 Catalyst Removal -- 10.5.2 Functional Group Tolerance -- 10.5.3 Substrate Purity -- 10.5.4 Catalyst Decomposition - Isomerization -- 10.6 Conclusion -- Biography -- References -- Chapter 11 Dehydrative Decarbonylation -- 11.1 Introduction -- 11.2 Use of Sacrificial Anhydride and Catalytic Mechanism -- 11.3 Rh‐, Pd‐, and Ir‐Catalysis -- 11.3.1 Early Studies -- 11.3.2 Recent Studies -- 11.4 Milder Temperatures -- 11.4.1 PdCl2/XantPhos/(tBu)4biphenol System -- 11.4.2 Well‐Defined Pd‐bis(phosphine) Precatalysts -- 11.5 Nickel and Iron Catalysis -- 11.6 Ester Decarbonylation -- 11.7 Synthetic Utility: -Vinyl Carbonyl Compounds -- 11.8 Conclusions and Future Prospects -- Biography -- References -- Index -- EULA.

Note: Cover -- Contents -- Preface -- List of Contributors -- Chapter 1 High-Oxidation State Molybdenum and Tungsten Complexes Relevant to Olefin Metathesis -- 1.1 Introduction -- 1.2 New Imido Ligands and Synthetic Approaches -- 1.3 Bispyrrolide and Related Complexes -- 1.4 Monoalkoxide Pyrrolide (MAP) Complexes -- 1.5 Reactions of Alkylidenes with Olefins -- 1.6 Olefin and Metallacyclopentane Complexes -- 1.7 Tungsten Oxo Complexes -- 1.8 Bisaryloxides -- 1.9 Other Constructs -- 1.10 Conclusions -- Acknowledgments -- References -- Chapter 2 Alkane Metathesis -- 2.1 Introduction -- 2.2 Alkane Metathesis by Single-Catalyst Systems -- 2.2.1 Supported Metal Hydrides -- 2.2.1.1 Supported Zr-Polyhydrides -- 2.2.1.2 Supported Ta-Polyhydrides -- 2.2.1.3 Supported W-Polyhydrides -- 2.2.2 Metal Alkylidene/Alkylidyne on Surface Oxide -- 2.2.2.1 Structure-Activity Relationship of Alkylidene Complexes -- 2.2.2.2 Stoichiometric Activity of Well-Defined, Metal Alkylidenes with Alkanes -- 2.2.2.3 Synthesis of Supported WMe6 on Silica -- 2.3 Alkane Metathesis by Tandem, Dual-Catalytic Systems -- 2.3.1 Introduction -- 2.3.2 The Chevron Process Using WO3/SiO2 and Pt-Li/Al2O3 -- 2.3.3 Tandem, Dual Catalytic System Using Ir-Pincer Ligands and Mo-Alkylidene Complexes -- 2.3.3.1 The Development of Robust, Iridium-Based Alkane Dehydrogenation Catalysts -- 2.3.3.2 Cyclic and Cross-Alkane Metathesis -- 2.4 Conclusion -- References -- Chapter 3 Diastereocontrol in Olefin Metathesis: the Development of Z-Selective Ruthenium Catalysts -- 3.1 Introduction -- 3.2 The Challenge of Z-Selective Olefin Metathesis -- 3.3 Previous Strategies -- 3.4 A Serendipitous Discovery -- 3.5 Catalyst Studies -- 3.5.1 Summary of Substituent Effects -- 3.5.1.1 Investigating the X-type Ligand -- 3.5.1.2 Effect of the NHC -- 3.5.2 Decomposition of Z-Selective Ru Metathesis Catalysts. , 3.6 Applications of Z-Selective Ru Metathesis Catalysts -- 3.6.1 Cross Metathesis -- 3.6.1.1 Homodimerization or Homocoupling -- 3.6.1.2 Other Cross-Metathesis Reactions -- 3.6.2 Ring-Closing Metathesis (RCM) -- 3.6.3 Ring-Opening Metathesis Polymerization (ROMP) -- 3.7 Conclusion -- References -- Chapter 4 Ruthenium Olefin Metathesis Catalysts Supported by Cyclic Alkyl Aminocarbenes (CAACs) -- 4.1 Introduction -- 4.2 Properties and Preparation of CAAC Ligands -- 4.3 CAAC-Supported, Ruthenium Olefin Metathesis Catalysts -- 4.3.1 CAAC Catalyst Development and Their Application to Ring-Closing Metathesis -- 4.3.2 Application to Cross Metathesis, Ethenolysis, and Degenerate Metathesis -- 4.4 Summary -- References -- Chapter 5 Supported Catalysts and Nontraditional Reaction Media -- 5.1 Introduction -- 5.2 Supported Catalyst Systems -- 5.2.1 Supported Catalysts via Covalent Interactions -- 5.2.1.1 Grubbs-Type, Ru-Based Systems -- 5.2.1.2 Schrock-Type, Mo- or W-Based Systems -- 5.2.2 Supported Catalysts via Non-covalent Interactions -- 5.2.2.1 Grubbs-Type, Ru-Based Systems -- 5.2.2.2 Early Transition-Metal Systems -- 5.3 Olefin Metathesis in Nontraditional Media -- 5.3.1 Olefin Metathesis in Water -- 5.3.1.1 Modified Catalyst Architectures -- 5.3.1.2 Commercially Available Catalysts -- 5.3.2 Olefin Metathesis in Ionic Liquids -- 5.3.2.1 Neutral Catalyst Systems -- 5.3.2.2 Ionic Modification to the Catalyst System -- 5.3.3 Olefin Metathesis in Fluorous Media -- 5.4 Conclusions -- References -- Chapter 6 Insights from Computational Studies on d0 Metal-Catalyzed Alkene and Alkyne Metathesis and Related Reactions -- 6.1 Introduction -- 6.2 Alkene Metathesis -- 6.2.1 Well-Defined Systems -- 6.2.1.1 Electronic Structure of M(ER1)(=CHR2)(X)(Y) Molecular Catalysts -- 6.2.1.2 Electronic Structure of Silica-Supported (≡SiO)M(ER1)(=CHtBu)(X) Catalysts. , 6.2.1.3 Electronic Structure of Metallacyclobutane Intermediates for the Molecular Catalysts -- 6.2.1.4 Alkene Metathesis Pathway for Well-Defined Catalysts -- 6.2.1.5 Deactivation and By-Product Formation Pathways for M(ER1)(=CHR2)(X)(Y) Catalysts -- 6.2.2 Classical, Heterogeneous Catalysts -- 6.2.2.1 MoO3 on Alumina -- 6.2.2.2 MoO3 on Silica -- 6.2.2.3 MoO3 on Zeolites -- 6.2.2.4 Re2O7 on Alumina and Silica: Alumina and Related Alumina-Supported CH3ReO3 Systems -- 6.3 Alkyne Metathesis -- 6.3.1 Group 6 M(***CR)(X)(Y)2 Alkylidyne Complexes in Alkyne Metathesis -- 6.3.2 Nitrile-Alkyne Cross Metathesis by the Reaction of W(N)X3 with 2-Butyne -- 6.4 Alkane Metathesis -- 6.4.1 Reactivity of Tantalum Hydrides -- 6.4.2 Reactivity of the Alumina-Supported, Bisalkyl Alkylidyne Tungsten Catalysts -- 6.5 Outlook -- References -- Chapter 7 Computational Studies of Ruthenium-Catalyzed Olefin Metathesis -- 7.1 Introduction -- 7.2 Computational Investigations of Non-Chelated Ruthenium Catalysts -- 7.2.1 Reaction Mechanisms -- 7.2.1.1 General Mechanism -- 7.2.1.2 Associative and Dissociative Mechanisms for Initiation -- 7.2.1.3 Initiation of Catalysts with Hemilabile Ligands -- 7.2.1.4 Bottom-Bound and Side-Bound Olefin Complexes -- 7.2.1.5 Structure of the Metallacyclobutane -- 7.2.2 Effects of Spectator Ligands -- 7.2.2.1 Stability of the Metallacyclobutane -- 7.2.2.2 Binding of Phosphine and Olefin Ligands -- 7.2.2.3 Rotameric Effects on the Alkylidene -- 7.2.2.4 Effect of Anionic Ligands -- 7.2.2.5 Summary of Ligand Effects -- 7.2.3 E/Z Selectivity -- 7.2.4 Reactivities of Substituted Olefins -- 7.2.5 Computations on Different Types of Olefin Metathesis Reactions -- 7.2.5.1 Ring-Opening Metathesis Polymerization -- 7.2.5.2 Ring-Closing Metathesis -- 7.2.5.3 Enyne Metathesis -- 7.2.6 Decomposition of Ruthenium Olefin Metathesis Catalysts. , 7.2.7 Alkene Isomerization -- 7.3 Computational Investigations of Chelated, Z-Selective Ruthenium Catalysts -- 7.3.1 Mechanism and Origins of Z Selectivity -- 7.3.2 Decomposition Pathways of the Chelated Ruthenium Catalysts -- 7.4 Accuracy of the Computational Methods -- References -- Chapter 8 Intermediates in Olefin Metathesis -- 8.1 Introduction -- 8.2 Metathesis-Active, Early-Metal Metallacycles -- 8.3 Intermediates in Ruthenium-Catalyzed Olefin Metathesis -- 8.3.1 Ruthenacyclobutane Intermediates Derived from Phosphonium Alkylidene Complexes -- 8.3.2 Ruthenacyclobutane Intermediates Derived from Bispyridyl Complexes -- 8.3.3 Ruthenium Alkylidene/Olefin Intermediates -- 8.4 Future Directions -- References -- Chapter 9 Factors Affecting Initiation Rates -- 9.1 Introduction -- 9.1.1 Discussion of General Terms -- 9.1.2 Experimental Measurement of Initiation Rates -- 9.2 Grubbs Second-Generation Catalyst -- 9.2.1 Phosphine Dissociation Related to Initiation and Metathesis Efficiency -- 9.2.2 Halide Substitution -- 9.2.3 Solvent Effects -- 9.2.4 Effect of Alkene Structure -- 9.3 Grubbs-Hoveyda-Type Precatalysts -- 9.4 Pyridine Solvates -- 9.5 Piers Catalysts -- 9.6 Indenylidene Carbene Precatalysts -- 9.7 Z-Selective Catalysts -- 9.8 Herrmann-Type, BisNHCs -- 9.9 Conclusions -- Acknowledgments -- References -- Chapter 10 Degenerate Metathesis -- 10.1 Introduction -- 10.2 Degenerate Metathesis Mechanisms -- 10.2.1 Potential Impact on Catalyst Efficiencies -- 10.3 Degenerate Metathesis with Early Transition-Metal Catalysts -- 10.3.1 Homogeneous, Early Transition-Metal Catalysts -- 10.3.2 Heterogeneous, Early Transition-Metal Catalysts -- 10.3.3 Conclusions on Degenerate Metathesis with Early Transition-Metal Catalysts -- 10.4 Degenerate Metathesis with Ruthenium Catalysts -- 10.5 Beneficial Effects of Degenerate Metathesis -- 10.6 Conclusions. , References -- Chapter 11 Mechanisms of Olefin Metathesis Catalyst Decomposition and Methods of Catalyst Reactivation -- 11.1 Introduction -- 11.2 Decomposition of Mo and W Imido Alkylidene Catalysts and Related Complexes -- 11.2.1 Mechanisms of Decomposition of Mo and W Systems -- 11.2.2 Strategies to Extend the Lifetime of Mo and W Catalysts -- 11.3 Decomposition of Ru Alkylidene Catalysts and Related Complexes -- 11.3.1 Thermal Decomposition of First-Generation Systems -- 11.3.2 Thermal Decomposition of Second-Generation Systems -- 11.3.3 Decomposition in the Presence of Small Molecules and Functional Groups -- 11.3.4 Strategies to Prevent the Decomposition of Ru Catalysts -- 11.3.5 Reactivation of Ruthenium Catalysts -- 11.4 Conclusions -- References -- Chapter 12 Solvent and Additive Effects on Olefin Metathesis -- 12.1 General Introduction -- 12.2 Solvent Effects on Olefin Metathesis -- 12.3 Additive Effects in Olefin Metathesis -- 12.4 Summary -- References -- Chapter 13 Metathesis Product Purification -- 13.1 Introduction -- 13.2 Chromatographic and Chemical Removal of Ruthenium -- 13.3 Removal by Complexation -- 13.4 Conclusion -- References -- Chapter 14 Ruthenium Indenylidene Catalysts for Alkene Metathesis -- 14.1 Introduction -- 14.2 The Initial Development of Indenylidene Metal Complexes for Alkene Metathesis -- 14.2.1 The Ruthenium Allenylidene Precursors -- 14.2.2 From Allenylidene to Indenylidene Ruthenium Complexes and Catalysts -- 14.2.3 Intramolecular Allenylidene-into-Indenylidene Rearrangements -- 14.3 Binuclear Indenylidene Ruthenium Catalysts Arising from Ruthenium(arene) Complexes -- 14.4 Preparation of Ruthenium Indenylidene Catalysts from RuCl2(PPh3)3 -- 14.4.1 First-Generation Ruthenium Indenylidene Catalysts Bearing Two Phosphine Ligands -- 14.4.2 First-Generation Ruthenium Indenylidene Catalysts Bearing a Chelating Ligand. , 14.4.2.1 First-Generation Ruthenium Indenylidene Catalysts Bearing a Bidentate Schiff Base Ligand.

Note: Cover -- Contents -- Preface -- List of Contributors -- List of Abbreviations -- Chapter 1 General Ring-Closing Metathesis -- 1.1 Introduction -- 1.2 Carbocycles (Introduction) -- 1.2.1 Small-Sized Carbocycles -- 1.2.2 Medium-Sized Carbocycles -- 1.2.3 Spiro Carbocycles -- 1.3 Synthesis of Bridged Bicycloalkenes -- 1.4 Synthesis of Heterocycles Containing Si, P, S, or B -- 1.4.1 Si-Heterocycles -- 1.4.2 P-Heterocycles -- 1.4.3 S-Heterocycles -- 1.4.4 B-Heterocycles -- 1.5 Synthesis of O-Heterocycles -- 1.5.1 Small and Medium-Size Cyclic Ethers -- 1.5.2 Polycyclic Ethers -- 1.6 Synthesis of N-Heterocycles -- 1.6.1 N-Heterocycles -- 1.6.2 Small and Medium-Sized Lactams -- 1.7 Synthesis of Cyclic Conjugated Dienes -- 1.8 Alkyne Metathesis -- 1.9 Enyne Metathesis -- 1.9.1 General Enyne Metathesis -- 1.9.2 Dienyne Metathesis -- 1.10 Tandem Processes -- 1.10.1 Tandem ROM/RCM -- 1.10.2 Other Tandem RCMs -- 1.11 Synthesis of Macrocycles -- 1.11.1 Macrocycles -- 1.11.2 Macrolactones -- 1.11.3 Macrolactams -- 1.12 RCM and Isomerization via Ru-H -- 1.13 Relay RCM (RRCM) -- 1.14 Z-Selective RCM -- 1.14.1 Substrate-Controlled Z-Selective RCM -- 1.14.2 Catalyst-Controlled Z-Selective RCM -- 1.15 Enantioselective RCM -- 1.16 Conclusion -- Acknowledgments -- References -- Chapter 2 Cross-Metathesis -- 2.1 Early Examples Using Well-Defined Molybdenum and Ruthenium Catalysts -- 2.2 The General Model for Selectivity in CM Reactions -- 2.3 Definition of Cross-Metathesis Reaction Categories and Chapter Organization -- 2.4 Hydrocarbons -- 2.4.1 Alkane Extensions -- 2.4.2 Unsaturated Hydrocarbons, Including Styrene -- 2.4.3 Ethylene Cross-Metathesis -- 2.5 Boron -- 2.6 Nitrogen -- 2.6.1 Amines -- 2.6.2 Amines as CM Partners in Heterocycle Syntheses -- 2.6.3 Acrylonitrile and Other Nitrile-Based CM Applications -- 2.6.4 Other Nitrogenous Substrates -- 2.7 Oxygen. , 2.7.1 Primary Allylic Alcohols and Derivatives -- 2.7.2 Secondary Allylic Alcohols and Derivatives -- 2.7.3 Tertiary Allylic Alcohols and Derivatives -- 2.7.4 Homoallylic Alcohols and Derivatives -- 2.7.5 Vinyl Ethers -- 2.7.6 Acrolein, Crotonaldehyde, and Methacrolein -- 2.7.7 Methyl Vinyl Ketone and Related Systems -- 2.7.8 Acrylic Acid -- 2.7.9 Acrylic Acid Derivatives, Including Esters, Thioesters, and Amides -- 2.8 Halides -- 2.9 Phosphorus -- 2.10 Sulfur -- 2.11 Fragment Coupling Reactions -- 2.11.1 Acetogenins -- 2.11.2 Cross-Metathesis Selectivity -- 2.11.3 Tuning Metathesis Selectivity -- 2.11.4 CM as an Alternative Coupling Strategy -- 2.11.5 CM-Based Analog Synthesis -- 2.11.6 Polyene Metathesis -- 2.11.7 Cross-Metathesis Reaction Optimization: Pinnaic Acid -- 2.12 Conclusions -- References -- Chapter 3 Vignette: Extending the Application of Metathesis in Chemical Biology - The Development of Site-Selective Peptide and Protein Modifications -- 3.1 Introduction -- 3.2 Cross-Metathesis Methodology Studies in Aqueous Media -- 3.2.1 Allyl Sulfides are Reactive Substrates in Olefin Metathesis -- 3.2.2 Sulfur-Relayed Cross-Metathesis -- 3.2.3 Application of Aqueous Metathesis of Allyl Sulfides in Synthesis -- 3.2.4 Cross-Metathesis of Se-Allyl Selenocysteine -- 3.3 Strategies for Allyl Chalogenide Incorporation into Proteins -- 3.3.1 Conjugate Addition to Dehydroalanine -- 3.3.2 Allyl Selenenylsulfide Rearrangement -- 3.3.3 S-Allyl Cysteine as a Methionine Surrogate -- 3.3.4 Other Genetic Incorporation Strategies -- 3.4 Olefin Metathesis on Proteins -- 3.4.1 Magnesium(II) is an Essential Additive in Olefin Metathesis on Proteins -- 3.4.2 Further Investigation of Allyl Ethers and Allyl Sulfides in RCM of Proteins and Peptides -- 3.4.3 Expanding the Scope of Cross-Metathesis on Proteins -- 3.5 Outlook -- References. , Chapter 4 Ruthenium-Catalyzed Tandem Metathesis/Non-Metathesis Processes -- 4.1 Introduction -- 4.2 Metathesis/Isomerization -- 4.2.1 RCM/Isomerization -- 4.2.2 Isomerization/RCM -- 4.2.3 CM/Isomerization -- 4.2.4 Enyne Metathesis/Isomerization -- 4.2.5 Isomerization/Enyne Metathesis -- 4.3 Metathesis/Hydrogenation -- 4.3.1 RCM/Hydrogenation -- 4.3.2 CM/Hydrogenation -- 4.4 Metathesis/Oxidation -- 4.4.1 RCM/Oxidative Aromatization -- 4.4.2 RCM/Allylic Oxidation -- 4.4.3 Metathesis/Hydroxylation -- 4.5 Metathesis/Cyclization -- 4.5.1 CM/aza-Michael Reaction -- 4.5.2 CM/oxa-Michael Reaction -- 4.5.3 CM/Conjugate Addition -- 4.5.4 CM/Conjugate Addition/Cyclization -- 4.5.5 RCM/Isomerization/Cyclization -- 4.6 Metathesis/Atom-Transfer Radical Addition -- 4.6.1 RCM/Kharasch Addition -- 4.6.2 CM/Kharasch Addition -- 4.6.3 Enyne Metathesis/Kharasch Addition -- 4.7 Metathesis/Rearrangement -- 4.7.1 Claisen Rearrangement/RCM -- 4.8 Metathesis/Cyclopropanation -- 4.8.1 Cyclopropanation/RCM -- 4.8.2 Enyne Metathesis/Cyclopropanation -- 4.8.3 CM/Cyclopropanation -- 4.8.4 RCM/Isomerization/Cyclopropanation -- 4.9 Metathesis/Miscellaneous -- 4.9.1 CM/Wittig Olefination -- 4.9.2 CM/Cycloaddition (Hetero-Pauson-Khand Reaction) -- 4.9.3 Enyne Metathesis/Hydrovinylation -- 4.9.4 Allylic Carboxylation/RCM -- 4.10 Conclusions -- References -- Chapter 5 Enyne Metathesis -- 5.1 Introduction -- 5.2 Enyne Metathesis -- 5.2.1 Brief Historical Background (1985-2002) -- 5.2.2 Mechanistic Studies and Selectivity Issues -- 5.2.2.1 Dichotomy of Mechanism - "Ene-First" or "Yne-First -- 5.2.2.2 Regioselectivity in Enyne Ring-Closing Metathesis -- 5.2.2.3 Regio and Stereoselectivity in Enyne Cross Metathesis -- 5.2.3 Enyne Metathesis and Metallotropic [1, 3] Shift (M& -- M) -- 5.2.4 Other Metal-Catalyzed Enyne Metatheses (Skeletal Reorganizations) -- 5.2.4.1 Introduction. , 5.2.4.2 Formation of Type-I exo Products -- 5.2.4.3 Formation of Type-II exo Products -- 5.2.4.4 Formation of endo Products -- 5.2.4.5 Miscellaneous -- 5.3 Strategic Application of Enyne Metathesis in Organic Synthesis -- 5.3.1 Enyne Metathesis -- 5.3.1.1 Enyne RCM in Synthesis of Carbocycles and Heterocycles -- 5.3.1.2 Enyne CM -- 5.3.1.3 Enyne Metathesis in Natural Products Synthesis -- 5.3.2 Tandem Enyne Metathesis -- 5.3.2.1 Dienyne Metathesis -- 5.3.2.2 Enyne RCM-CM Sequence -- 5.3.2.3 Enyne Ring-Rearrangement Metathesis (RRM) -- 5.3.2.4 Multiple Enyne Metathesis -- 5.3.2.5 Enyne CM-RCM Sequence -- 5.3.3 Tandem Enyne Metathesis-Diels-Alder Reaction Sequences -- 5.3.3.1 Enyne Metathesis-Intermolecular Diels-Alder Reaction -- 5.3.3.2 Enyne Metathesis-Intramolecular Diels-Alder Reaction -- 5.3.4 Other Tandem Enyne Metathesis Sequences -- 5.4 Perspective -- References -- Chapter 6 Alkyne Metathesis -- 6.1 Introduction -- 6.2 Background Information -- 6.3 Molybdenum Alkylidyne Catalysts with Silanolate Ligands -- 6.3.1 General -- 6.3.2 Representative Procedure: Ring-Closing Alkyne Metathesis with the Aid of a Bench-Stable Molybdenum Alkylidyne Adduct -- 6.3.3 Molybdenum Nitrides as Precatalysts -- 6.3.4 Structural and Mechanistic Aspects -- 6.4 Other Catalytically Active Molybdenum Alkylidyne Complexes -- 6.5 Novel Tungsten Alkylidyne Catalysts -- 6.6 Basic Types of Applications -- 6.6.1 Alkyne Self-Metathesis and Cyclo-Oligomerization Reactions -- 6.6.2 Oligomerization and Polymerization Reactions -- 6.6.3 Alkyne Cross Metathesis -- 6.6.4 Ring-Closing Alkyne Metathesis -- 6.6.5 Metathesis of Terminal Alkynes -- 6.7 Selected Applications -- 6.7.1 Organometallic Substrates -- 6.7.2 Olfactory Macrocycles -- 6.7.3 Cruentaren A -- 6.7.4 Haliclonacyclamine C -- 6.7.5 Nakadomarin A -- 6.7.6 Prostaglandins and Oxylipins -- 6.7.7 Neurymenolide A. , 6.7.8 Tulearin C -- 6.7.9 Stereoselective Syntheses of 1,3-Dienes by RCAM/Semireduction: Total Syntheses of Latrunculin, Lactimidomycin, and Leiodermatolide -- 6.7.10 Amphidinolide V -- 6.7.11 Citreofuran -- 6.7.12 Polycavernoside A -- 6.7.13 Amphidinolide F -- 6.7.14 Spirastrellolide F -- 6.8 Conclusions -- References -- Chapter 7 Catalyst-Controlled Stereoselective Olefin Metathesis -- 7.1 Introduction -- 7.2 Enantioselective Ring-Opening/Cross-Metathesis (EROCM) -- 7.2.1 Reactions with Chiral Ru Carbenes -- 7.2.2 Reactions with Chiral Mo-Based Biphenolates -- 7.2.3 Reactions of Azabicycles: Ru- versus Mo-Based Catalysts -- 7.2.4 Application to Enantioselective Synthesis of a Natural Product -- 7.3 Enantioselective Ring-Opening/Ring-Closing Metathesis (ERORCM) -- 7.4 Enantioselective Ring-Closing Metathesis (ERCM) -- 7.4.1 Reactions with Chiral Ru-Based Complexes -- 7.4.2 ERCM Reactions with Chiral Mo-Based Diolates -- 7.4.2.1 Synthesis of N-Heterocycles -- 7.4.2.2 Synthesis of Cyclic Alkenyl Ethers -- 7.4.2.3 Synthesis of Cyclic Alkenes with a P-Stereogenic Center -- 7.4.2.4 Control of Planar Stereogenicity -- 7.4.3 Reactions with Monopyrrolide-Aryloxide (MAP) Stereogenic-at-Mo Complexes -- 7.4.3.1 Catalyst Design, ERCM Reactions, and Application to Total Synthesis of Quebrachamine -- 7.4.3.2 Enantioselective Enyne RCM -- 7.5 Z-Selective Olefin Metathesis Reactions with Mo- and W-Based Complexes -- 7.5.1 Reactions with Chiral Mo-Based Diolates: Net Enantio- and Z-Selective Cross-Metathesis (CM) -- 7.5.2 Reactions with Mo- and W-Based Monopyrrolide Aryloxide (MAP) Complexes -- 7.5.2.1 Catalytic Enantio- and Z-Selective Ring-Opening/Cross-Metathesis (ROCM) -- 7.5.2.2 Catalytic Z-Selective Homo-Coupling -- 7.5.2.3 Catalytic Z-Selective Cross-Metathesis (CM) -- 7.5.2.4 Pure E-Alkenes by Catalytic Z-Selective Ethenolysis. , 7.5.2.5 Catalytic Z-Selective Macrocyclic Ring-Closing Metathesis (RCM).

Note: Cover -- Contents -- Preface -- List of Contributors -- Chapter 1 Synthesis of Homopolymers and Copolymers -- 1.1 Introduction -- 1.2 Initiators -- 1.3 Monomers -- 1.4 Synthesis of Polymers with Complex Architectures -- 1.5 Stereochemistry and Sequence Control in ROMP -- 1.6 Conclusion -- References -- Chapter 2 ROMP in Dispersed Media -- 2.1 Introduction -- 2.2 Emulsion ROMP -- 2.2.1 Mini-emulsion ROMP -- 2.2.2 Micro-emulsion ROMP -- 2.2.3 Micellar ROMP -- 2.2.4 ROMP in Nonaqueous Emulsions -- 2.3 Dispersion ROMP -- 2.3.1 Biomedical Applications of PNBE-PEO Core-Shell Nanoparticles -- 2.4 Suspension ROMP -- 2.5 Formation of Nanoparticles -- 2.5.1 Photoactive ROMP Assemblies -- 2.5.2 Miscellaneous -- 2.6 Conclusion -- References -- Chapter 3 Telechelic Polymers -- 3.1 Introduction -- 3.2 Mono-telechelic Polymers -- 3.2.1 Reaction with Substituted Vinyl Ethers -- 3.2.2 Vinyl Lactone Quenching -- 3.2.3 Terminal Cross Metathesis -- 3.2.3.1 Using Symmetrical Olefins -- 3.2.3.2 Using Asymmetrical Olefins -- 3.2.4 Reaction with Oxygen -- 3.2.5 Sacrificial Diblock Copolymer Synthesis -- 3.2.6 Catalyst Prefunctionalization -- 3.2.6.1 Functional Catalysts from Precursor Complexes -- 3.2.6.2 Functional Catalysts via Cross Metathesis -- 3.2.7 Aldehyde Quenching -- 3.3 Homo-telechelic Polymers -- 3.3.1 Degradation of Unsaturated Polymers and ADMET Polymerization -- 3.3.2 ROMP/Chain Transfer -- 3.3.3 Sacrificial Multiblock Copolymers -- 3.4 Hetero-telechelic Polymers -- 3.4.1 Prefunctionalization with Functional Alkylidene Initiators -- 3.4.2 Prefunctionalization with Sacrificial Synthesis -- 3.5 Conclusions and Outlook -- Acknowledgments -- References -- Chapter 4 Supramolecular Polymers -- 4.1 Introduction -- 4.2 Main-Chain Supramolecular Polymers -- 4.2.1 Macromonomers -- 4.2.2 ABC Triblock Copolymers. , 4.3 Side-Chain-Functionalized Supramolecular Polymers -- 4.3.1 Hydrogen-Bonding Recognition Motifs -- 4.3.2 Metal Coordination-Based Recognition Motifs -- 4.3.3 Mixed Orthogonal Recognition Motifs -- 4.4 Supramolecular Architectures by Design -- 4.5 Conclusion -- References -- Chapter 5 Synthesis of Materials with Nanostructured Periodicity -- 5.1 Introduction -- 5.2 Sequential ROMP -- 5.3 Inorganic Composite Materials -- 5.4 ABA Triblock Copolymers -- 5.5 Nanostructures with Domain Sizes Exceeding 100 nm -- 5.6 Conclusions -- References -- Chapter 6 Synthesis of Nanoparticles -- 6.1 Introduction -- 6.2 Formation of Nanoparticles -- 6.3 Synthesis via Grafting-through Approach -- 6.4 Synthesis via Grafting-to Approach -- 6.4.1 Grafting-to Polymer Backbones via an Activated Ester -- 6.4.2 Grafting-to Polymer Backbones via Copper-Catalyzed Click Reaction -- 6.5 Synthesis via Grafting-from Approach -- 6.6 Summary -- References -- Chapter 7 Synthesis of Biodegradable Copolymers -- 7.1 Introduction -- 7.2 Polyester-Functionalized Polymers -- 7.3 Peptide-Functionalized Polymers -- 7.4 Carbohydrate-Functionalized Polymers -- 7.5 Antimicrobial Polymers -- 7.6 Polymeric Betaines -- 7.7 ROMP Polymers as Drug Carriers -- 7.8 ROMP Polymers for Tissue Scaffolds -- 7.9 Conclusion -- References -- Chapter 8 Biologically Active Polymers -- 8.1 Introduction -- 8.2 Benefits of ROMP for Bioactive Polymer Synthesis -- 8.3 Biologically Active Polymeric Displays -- 8.3.1 Catalyst Design -- 8.3.2 Monomer Design for Bioactive Polymers -- 8.3.3 Troubleshooting in Polymerization of Bioactive Monomers -- 8.3.4 Routes to Functionalized Polymers -- 8.4 Exploiting the Bulk Properties of Polymers -- 8.4.1 Hydrogels -- 8.4.2 Coatings -- 8.4.2.1 Nonfouling Surfaces -- 8.4.2.2 Antimicrobial Peptides -- 8.4.2.3 Integrin-Binding Materials for Cell Adhesion and Spreading. , 8.4.2.4 Biolubricants -- 8.4.3 Drug Delivery -- 8.4.3.1 Self-Assembled Polymer Nanoparticles -- 8.4.3.2 Bottlebrush ROMP Polymers -- 8.4.4 Analytical Tools for Biodetection -- 8.4.4.1 On-Chip Assays -- 8.4.4.2 Imaging Agents -- 8.5 Probes of Biological Processes -- 8.5.1 Inhibitors -- 8.5.1.1 The Selectins and the Inflammatory Response -- 8.5.1.2 Integrins and Cellular Adhesion -- 8.5.1.3 GAG Surrogates -- 8.5.2 Effectors -- 8.5.2.1 Chemotaxis -- 8.5.2.2 Multivalent Antigens in B-Cell Signaling -- 8.5.3 Cell Penetration Polymers -- 8.5.3.1 Translocation Domains and Polyplexes -- 8.5.3.2 Targeted Delivery: B Cell Internalization -- 8.5.4 Assembling Multiprotein Complexes -- 8.5.4.1 Regulation of Immune Responses -- 8.6 Outlook -- References -- Chapter 9 Combination of Olefin Metathesis Polymerization with Click Chemistry -- 9.1 Introduction -- 9.2 Attaching Functional Groups for Click Reaction -- 9.2.1 Alkyne(s) -- 9.2.2 Azide(s) -- 9.2.3 Thiol(s) -- 9.2.4 Acrylate(s)/Maleimide(s) -- 9.2.5 Anthracene(s) -- 9.2.6 Click Reaction before ROMP -- 9.3 Copper-Catalyzed Azide/Alkyne Click Reaction -- 9.3.1 Polymers with Hydrogen-Bonding Motifs -- 9.3.2 Biomedical Applications -- 9.3.3 Complex Polymeric Architectures via Azide/Alkyne Click Chemistry -- 9.3.4 Grafting-from and Catalyst Design -- 9.4 Diels-Alder Click Reaction -- 9.5 Thiol-Ene Reaction -- 9.6 Thiol-Michael Addition -- 9.7 Meldrum's Acid-Containing Polymers as Precursor for Ketene Coupling -- 9.8 Nitrile Oxide Cycloaddition -- Acknowledgment -- References -- Chapter 10 Self-Healing Polymers -- 10.1 Introduction -- 10.2 Monomer Storage -- 10.2.1 Encapsulation -- 10.2.2 Monomer-Filled Discreet and Connected Channels -- 10.3 Catalyst Stability and Protection -- 10.4 Catalyst and Monomer Choice -- 10.4.1 Pre-macroscopic Gelation: Monomer Delivery and Catalyst Dissolution. , 10.4.2 Pre-vitrification: Catalyst Diffusion and Polymerization -- 10.4.3 Post-vitrification: Healed Polymer -- 10.5 Intrinsic Self-Healing Polymers -- 10.5.1 Mechanochemical Activation of Alkylidene Ruthenium Complexes -- 10.5.2 Dynamic Cross-Metathesis in Unsaturated Polymers -- 10.6 Conclusions -- References -- Chapter 11 Functional Supports and Materials -- 11.1 Introduction -- 11.2 Preparation of Functional Supports -- 11.2.1 Precipitation Polymerization Methods -- 11.2.2 Grafting Techniques -- 11.2.3 Coating Techniques -- 11.2.4 Nanoparticle Loading -- 11.3 Functional Monolithic Supports -- 11.3.1 Concepts -- 11.3.2 Synthesis of Monolithic Supports -- 11.3.3 Functionalization, Metal Removal, and Metal Content -- 11.3.4 Applications -- 11.3.4.1 Catalysis -- 11.3.4.2 Separation Science -- 11.3.4.3 Tissue Engineering -- 11.4 Twenty-First Century Functional Supports -- 11.5 Summary and Outlook -- Acknowledgment -- References -- Chapter 12 Latent Ruthenium Catalysts for Ring Opening Metathesis Polymerization (ROMP) -- 12.1 Introduction -- 12.2 Thermal Activation -- 12.2.1 Cis-Dianion Type Catalysts -- 12.2.2 Catalysts Bearing Electron-Rich Carbene Ligands -- 12.2.3 Catalysts Bearing Chelating Ligands -- 12.3 Light-Induced Activation -- 12.4 Chemical Activation -- 12.5 Mechanical Activation -- 12.6 Conclusions -- References -- Chapter 13 ADMET Polymerization -- 13.1 Introduction -- 13.2 ADMET: The Metathesis Polycondensation Reaction -- 13.2.1 Implications of Step Growth -- 13.2.2 Cyclization versus Polymerization -- 13.2.3 Interchange Reactions -- 13.2.4 Monomer Purity -- 13.2.5 Catalyst Considerations -- 13.2.5.1 Isomerization -- 13.2.5.2 Catalyst Activity and Functional Group Tolerance -- 13.2.6 Solvent -- 13.2.7 Hydrogenation -- 13.3 ADMET of Nonconjugated Hydrocarbon Dienes -- 13.3.1 Terminal Dienes -- 13.3.2 Branched Terminal Dienes. , 13.3.3 1,1-Disubstitued Olefins -- 13.3.4 1,2-Disubstituted Olefins -- 13.3.5 Trisubstituted Olefins -- 13.4 ADMET Copolymerization -- 13.5 ADMET of Functionalized Dienes -- 13.5.1 Ethers, Acetals, and Alcohols -- 13.5.2 Amines -- 13.5.3 Thioethers -- 13.5.4 Carbonyl Compounds -- 13.5.5 Negative Neighboring Group Effect -- 13.5.6 Halides -- 13.5.7 Carboxylic and Phosphonic Acids -- 13.5.8 Silicon Compounds -- 13.5.9 Ionomers -- 13.5.10 Organometallic Compounds -- 13.6 Functional Materials -- 13.6.1 Biological Applications -- 13.6.2 Electroactive Polymers -- 13.6.3 Liquid-Crystalline Polymers -- 13.7 Modeling Polyethylene -- 13.7.1 Modeling Branching in Polyethylene -- 13.7.2 Modeling Copolymers of Ethylene and Vinyl Monomers -- 13.8 Conjugated Polymers -- 13.8.1 Polyacetylenes -- 13.8.2 Poly(phenylene vinylene)s -- 13.8.3 Poly(thienylene vinylene) -- 13.8.4 Other Conjugated Polymers -- 13.9 Solid-State Polymerization -- 13.10 ADMET Depolymerization -- 13.11 Telechelic Oligomers -- 13.12 Complex Polymer Architectures -- 13.12.1 Hyperbranced Polymers -- 13.12.2 Mechanically Interlocked Polymers -- 13.13 Biorenewable Polymers -- 13.14 Conclusions and Outlook -- References -- Chapter 14 Biorenewable Polymers -- 14.1 Introduction -- 14.2 ADMET -- 14.2.1 Plant Oils -- 14.2.2 Postmodification -- 14.2.3 Acyclic Triene Metathesis (ATMET) -- 14.2.4 Specialized Polymers -- 14.2.4.1 Polymers for Isomerization Studies -- 14.2.4.2 Phosphorus-Containing Polymers -- 14.2.4.3 Nylon -- 14.3 ROMP -- 14.3.1 Castor Oil -- 14.3.2 Dilulin -- 14.3.3 Norbornyl-Modified Fatty Acids -- 14.3.4 Terpenes -- 14.4 Conclusion -- References -- Chapter 15 Polymerization of Substituted Acetylenes -- 15.1 Introduction -- 15.2 Polymerization Reactions -- 15.3 Catalysts -- 15.4 Recent Catalysts for Living Polymerization -- 15.4.1 Metal Halide-Based Catalysts. , 15.4.2 Single-Component Catalysts.