Ruthenium catalyzed olefin metathesis double bond isomerization sequence

Chauvin's experimental evidence was based on the reaction of cyclopentene and 2-pentene with the homogeneous catalyst tungsten VI oxytetrachloride and tetrabutyltin: Cyclic ruthenium-alkylidene catalysts for ring-expansion metathesis polymerization. Blechert, Experimental Section Angew.


It is reasoned that an alkene part in product 12h further reacts with ruthenium carbene methylidene complex 1l to afford ruthenium carbene 14, which would be coordinated by the alkene part to produce We have already shown that important efficiency improvements in the cross-metathesis of unsaturated fatty acid derivatives with acrylonitrile were obtained when the catalyst was slowly added to the reaction mixture.

The Thorpe—Ingold effect may also be exploited to improve both reaction rates and product selectivity. A powerful family of Z-selective olefin metathesis catalysts Topics in Organometallic Chemistry.

The first catalyzed metathesis reactions were observed in the late's when chemists at DuPont, Standard Oil, and Phillips Petroleum reported the metathesis of propene with catalysts based on molybdenum and tungsten. General Procedure for Macrocyclizations Using Catalyst 9 In a glovebox, a mL Strauss flask was charged with a solution of diene 1 equiv, ca.

Prominent among these initiators are Schrock's four-coordinate alkoxy imido complexes of molybdenum with a bulky aryl substituent on the imido group and bulky, electron withdrawing alkoxide ligands which, as already pointed out, provide steric shield and contribute to increase the electrophilicity of the metal center.

General Procedure for Homodimerization Reactions In a glovebox, a 4 ml vial was charged with catalyst 0.

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Conditions could always be found to reach complete conversion of the substrate 17 and in all cases the addition of 1,4-benzoquinone was found beneficial and improved the isolated yields of the expected products.

Using the most reactive metal-carbene species known at that time, pentacarbonyl diphenylmethylene tungsten, he successfully polymerized strained and low-strain cycloolefins with remarkably high stereoselectivities.

Origins of initiation rate differences in ruthenium olefin metathesis catalysts containing chelating benzylidenes.

The remarkable metal-catalysed olefin metathesis reaction

The reverse reaction of CM of two alpha-olefins, ethenolysiscan be favored but requires high pressures of ethylene to increase ethylene concentration in solution. Since its discovery in the s, metathesis has been employed with great success in a number of fields, including biochemistry, materials science, and green chemistry see a Binder, J.

Complexes 1b and 1c are stable and easy to handle Figure 1. With Ru and Os, a low coordination number of the metal usually results in catalytic metathesis activity, whereas high coordination number complexes lead to stoichiometric cyclopropanation.

All reactions were carried out in dry glassware under an argon atmosphere using standard Schlenk techniques or in a Vacuum Atmospheres Glovebox under a nitrogen atmosphere, unless otherwise specified.

Synthesis and thermolysis of Ir I fischer carbenes Organometallics. Homodimerization of Methyl Undecenoate 13 and 4-Pentenol Improving brush polymer infrared one-dimensional photonic crystals via linear polymer additives.

Olefin metathesis

The solution was dried with MgSO4, filtered, and concentrated. Having established the effectiveness of 9 in homodimerization reactions, we set about to further evaluate its activity and Z-selectivity by exploring more complex transformations.

From methyl methacrylate the best yields were obtained in neat conditions, and for the cross-metathesis with acrylonitrile and acrylamides the slow addition of the catalyst proved to be the most convenient procedure.

July 10, ; Angew. Likewise, Bob Grubbs used a pragmatic approach, from RuCl 3 in water to the sophisticated chiral version of the second generation ruthenium benzylidene catalyst, to provide the organic and polymer communities with what are now the most environmentally friendly metathesis catalysts, because of their stability to air and even to some extent to aqueous media and their high compatibility with most organic functionalities.

Scope of The Reaction Many olefinic substrates can undergo metathesis to afford an extensive range of new unsaturated products.

Figure 2, the profiles for reactions carried out in DMC are Next, cross-metathesis of 1-decene and methyl acrylate was almost identical to those carried out in dichloromethane.

separation of ruthenium impurities is important as ruthenium residues can lead to undesirable side-reactions like hydrogenation or alkene isomerization in reaction products [8,9].

There are several ways to approach the three issu es noted above. Perhaps the simplest approach is to simply reduce the amount of catalyst that is used in the reaction.

Ruthenium olefin metathesis

Protonolysis of a ruthenium-carbene bond and applications in olefin metathesis. Prevention of undesirable isomerization during olefin metathesis. Journal of the American Chemical Society.

Decomposition of a key intermediate in ruthenium-catalyzed olefin metathesis reactions. Current Literature. Guidelines for Current Literature group meetings: • students will present a recent (published within the last 4 months) communication or article (no reviews or perspectives) each of eminent interest to our research and/or of general high significance for the field of chemistry or biology.

The transition-metal catalyzed olefin metathesis reaction has emerged as an indispensable methodology for the construction of new carbon-carbon double bonds.1 Since its discovery in the s, metathesis has been employed with great success in a number of fields, including biochemistry,2 materials science,3 and green chemistry.4 However, an ongoing.

REVIEWS The remarkable metal-catalysed olefin metathesis reaction Amir H. Hoveyda1 & Adil R.

WO2014093687A1 - Z-selective metathesis catalysts - Google Patents

Zhugralin1 Catalytic olefin metathesisâthrough which pairs of C5C bonds. The most important reaction of these alkylidene complexes is undoubtedly olefin metathesis, a redistribution of the carbon groups joined by double (or triple) bonds.

Applications of this reaction range from novel polymerizations to selective carbo and heterocyclic ring formation.

Ruthenium catalyzed olefin metathesis double bond isomerization sequence
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