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Acyclic diene metathesis
About: Acyclic diene metathesis is a research topic. Over the lifetime, 1903 publications have been published within this topic receiving 81665 citations.
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01 Jan 1997
TL;DR: The metal carbene/metallacyclobutane mechanism has been studied extensively in the literature as mentioned in this paper, with a focus on the use of a ring-opening metathesis.
Abstract: 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 [M 2]/[M 1]. 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.
841 citations
TL;DR: Olefin metathesis as discussed by the authors is a metal-catalyzed exchange of alkylidene moieties between alkenes, which can induce both cleavage and formation of CC double bonds.
Abstract: Transition metal catalyzed CC bond formations belong to the most important reactions in organic synthesis. One particularly interesting reaction is olefin metathesis, a metal-catalyzed exchange of alkylidene moieties between alkenes. Olefin metathesis can induce both cleavage and formation of CC double bonds. Special functional groups are not necessary. Although this reaction—which can be catalyzed by numerous transition metals—is used in industry, its potential in organic synthesis was not recognized for many years. The recent abrupt end to this Sleeping-Beauty slumber has several reasons. Novel catalysts can effect the conversion of highly fictionalized and sterically demanding olefins under mild reaction conditions and in high yields. Improved understanding of substrate–catalyst interaction has greatly contributed to the recent establishment of olefin metathesis as a synthetic method. In addition to the preparation of polymers with fine-tuned characteristics, the metathesis today also provides new routes to compounds of low molecular weight. The highly developed ring-closing metathesis has been proven to be key step in the synthesis of a growing number of natural products. At the same time interesting applications can be envisioned for newly developed variants of bimolecular metathesis. Improvements in the selective cross-metathesis of acyclic olefins as well as promising attempts to include alkynes as viable substrates provide for a vivid development of the metathesis chemistry.
745 citations
704 citations
TL;DR: Several ruthenium-based olefin metathesis catalysts of the formula (PR3)2X2RuCHCHCPh2 have been synthesized, and relative catalyst activities were determined by monitoring the ring-closing met athesis of the acyclic diene diethyl diallylmalonate as discussed by the authors.
Abstract: Several ruthenium-based olefin metathesis catalysts of the formula (PR3)2X2RuCHCHCPh2 have been synthesized, and relative catalyst activities were determined by monitoring the ring-closing metathesis of the acyclic diene diethyl diallylmalonate. The following order of increasing activity was determined: X = I < Br < Cl and PR3 = PPh3 ≪ PiPr2Ph < PCy2Ph < PiPr3 < PCy3. Additional studies were conducted with the catalyst (PCy3)2Cl2RuCH2 to probe the mechanism of olefin metathesis by this class of catalysts. The data support a scheme in which there are two competing pathways: the dominant one in which a phosphine dissociates from the ruthenium center and a minor one in which both phosphines remain bound. Higher catalyst activites could be achieved by the addition of CuCl to the reaction.
631 citations