In recent years, the olefin metathesis reaction has attracted widespread attention as a versatile carbon−carbon bond-forming method. Many new applications have become possible because of major advances in catalyst design. State-of-the-art ruthenium catalysts are not only highly active but also compatible with most functional groups and easy to use. This Account traces the ideas and discoveries that were instrumental in the development of these catalysts, with particular emphasis on (PCy3)2Cl2RuCHPh and its derivatives. The discussion includes an analysis of trends in catalyst activity, a description of catalysts coordinated with N-heterocyclic carbene ligands, and an overview of ongoing work to improve the activity, stability, and selectivity of this family of L2X2RuCHR complexes.

http://web4.uwindsor.ca/users/j/jlichaa/reference.nsf/0/10ff8b04ff3a317885256d88005720f6/$FILE/acr-2001-34-18-metath-grubbs.pdf

The Development of L2X2RuCHR Olefin Metathesis Catalysts: An Organometallic Success Story

Recent advances in olefin metathesis and its application in organic synthesis

The fascinating story of olefin (or alkene) metathesis (eq
1) began almost five decades ago, when Anderson and
Merckling reported the first carbon-carbon double-bond
rearrangement reaction in the titanium-catalyzed polymerization of norbornene. Nine years later, Banks and Bailey reported “a new disproportionation reaction . . . in which olefins are converted to homologues of shorter and longer carbon chains...”. In 1967, Calderon and co-workers named this metal-catalyzed redistribution of carbon-carbon double bonds olefin metathesis, from the Greek word “μeτάθeση”, which means change of position. These contributions have since served as the foundation for an amazing research field, and olefin metathesis currently represents a powerful transformation in chemical synthesis, attracting a vast amount of interest both in industry and academia.

https://core.ac.uk/download/pdf/4884240.pdf

Ruthenium-based heterocyclic carbene-coordinated olefin metathesis catalysts.

We gratefully acknowledge funding and support from King Abdullah University of Science and Technology (KAUST). Thanks are also due to the KAUST communication department for designing several images for this Review.

Magnetically recoverable nanocatalysts.

Living ring-opening 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 [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.

I. C Mol

Papers

Olefin metathesis and metathesis polymerization