Olefin Metathesis and Metathesis Polymerization

Preface. Abbreviations. Introduction: The Olefin Metathesis Reaction. Brief History. The Metal Carbene Mechanism. Equilibria and Stereoselectivity. Survey of Catalyst Systems: Group IV. Group V. GroupVI. Group VII. Group VIII. Photochemically Activated Catalysts. The Metal Carbene/Metallacyclobutane Mechanism: Evidence from Cross-Metathesis Reactions. Evidence from the Stereochemistry of Metathesis of Internal Olefins. Evidence from Ring-Opening Metathesis Polymerization (ROMP). Evidence from the reactions of Well-Defined Metal Carbene Complexes. Evidence from the Reactions of Metallacyclobutane Complexes. Evidence of Initiating Species in Systems with Non-Carbene Catalysts. Theoretical Treatments. Related Reactions: [2+2] Reactions Between Compounds Containing Multiple Bonds. Relationship to Ziegler-Natta Polymerization. Involvement of Three-Membered Ring Compounds in Metathesis Reactions. Ethene and Terminal Alkenes: Ethene. Propene. But-1-ene and its Derivatives. Pent-1-ene and its Derivatives. Hex-1-ene and its Derivatives. Higher Acyclic Terminal Alkenes. Acyclic Disubstituted and Trisubstituted Ethenes. Cis/trans Isomerization. Pent-2-ene and 4-Substituted Derivatives. Hex-2-ene and 4-Methylhex-2-ene.Hept-2-ene and Hept-3-ene. Higher Acyclic Internal Olefins. Stereoselectivity in the Metathesis of Acyclic Olefins. 1,1-Disubstituted Olefins. Trisubstituted Ethenes. Acyclic Functionalized Alkenes: Esters. Other Carbonyl-Containing Compounds. Ethers. Amines. Nitriles. Chlorides and Bromides. Sulfides and Sulfonates. Silancs and Germanes. Phospanes. Acyclic Dienes: Double Bonds Linked only by C Atoms. Double Bonds Linked by C and Si, Ge orSn Atoms. Double Bonds Linked by C and N Atoms. Double Bonds Linked by C, Si, and O Atoms. Divinylferrocene. Some Further Applications in Organic Synthesis. Copolymers by Metathesis Condensation. Cross-Metathesis Between Acyclic Compounds: Ethene.Propene. Butenes. Pentenes. Hexenes. Higher Olefins. Functionalized Olefins. Acetylenes: Metathesis Reactions Involving Total Cleavage of the C=C bond. Metathesis Reactions Involving Cleavage of Two of the thress C=C Bonds. Metathesis Reactions of Enynes and Dienynes. Other Metathesis Routes to Polyacetylenes. Ring-Opening Metathesis Polymerization: General Aspects: Thermodynamic Aspects. Efficiency of Initiation. The Use of Chain-Transfer Agents. Molecular Weight Distributions. Polymer Micostructure. Monocyclic Alkenes and Polyenes: Four-Membered Rings. Five-Membered Rings. Six-Membered Rings. Seven-Membered Rings. Eight-Membered Rings. Nine-Membered Rings. Ten-Membered Rings. Twelve-Membered and Other Rings. Polycyclic Alkenes: Monomers Containing a Fused Cyclobutene Ring. Monomers Containing a Fused Cyclopentene Ring and One Double Bond. Monomers Containing a Fused Cyclopentene Ring and More than One Double Bond. Bicyclo[2.2.1] Compounds Containing Heteroatoms in the Ring System. Other Bicyclic Compounds. Copolymers of Cycloalkenes: Direct Metathesis Copolymerization. Cyclic Co-Oligomers. Block Copolymers by Sequential Addition of Monomers to Living Systems. Block Copolymers by Modification of Homopolymers. Comb and GraftCopolymers. Copolymers by ROMP in Conjunction with Radical Reactions. Cross-Metathesis Between Cyclic and Acyclic Olefins: End-Groups and Telomers. Dependence of Molecular Weight on [M2]/[M1]. Kinetic Data. Degradation of UnsaturatedPolymers by Metathesis: Degradation by Intramolecular Metathesis. Applications of the Olefin Metathesis Reaction: The Phillips Triolefin Process. The Neohexene Process. The Shell Higher Olefins Process. Other Multistage Processes Involving Metathesis. The Isoamylene Process. (Circle around alpha and omega) ((-Diolefins. trans-Poly(1-Pentenylene). trans-Poly(1-octenylene). Polymers of Norhornene. Polymers of Norbornene Derivatives. Miscellaneous. Bibliography. Subject Index.