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Unsaturated halocarbene complexes can be synthesized in the first example of olefin metathesis with a directly fluorinated substrate. The ruthenium catalyst 1 reacts with 1,1-difluoroethylene to yield the corresponding methylidene [Ru] = CH2 (2) and difluorocarbene [Ru] = CF2 complexes (3). H2IMes = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene; Cy = cyclohexyl.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Extracurricular laboratory:new discovery of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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The design, development and application of an efficient procedure for the concise synthesis of the 1,3-syn- and anti-tetrahydropyrimidine cores of manzacidins are reported. The intramolecular allylic substitution reaction of a readily available joint urea-type substrate enables the facile preparation of both diastereomers in high yields. The practical application of this approach is demonstrated in the efficient and modular preparation of the authentic heterocyclic cores of manzacidins, structurally unique bromopyrrole alkaloids of marine origin. Additional features of this route include the stereoselective generation of the central amine core with an appending quaternary center by an asymmetric addition of a Grignard reagent to a chiral tert-butanesulfinyl ketimine following an optimized Ellman protocol and a cross-metathesis of a challenging homoallylic urea substrate, which proceeds in good yields in the presence of an organic phosphoric acid.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

A new application about (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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A ruthenium-catalyzed transfer hydrogenation of olefins utilizing formic acid as a hydrogen donor is described. The application of commercially available alkylidene ruthenium complexes opens access to attractive C(sp3)-C(sp3) bond formation in an olefin metathesis/transfer hydrogenation sequence under tandem catalysis conditions. High chemoselectivity of the developed methodology provides a remarkable synthetic tool for the reduction of various functionalized alkenes under mild reaction conditions. The developed methodology is applied for the formal synthesis of the drugs pentoxyverine and bencyclane.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Discovery of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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A Hoveyda-type catalyst for olefin metathesis was synthesized and covalently attached via an amide bond to four different solid supports. One of these supports was a home-made hybrid silica support, where an ultra-thin copolymer of poly(styrene) and poly(acrylamide) was grafted on. The three other supports were commercially available, namely HypoGel 400, PEGA and Trisoperl. It was demonstrated that the catalysts were active in ring closing metathesis (RCM) reactions as well as in cross metathesis (CM) and ring opening metathesis (ROM) reactions, but the activity of the catalyst was highly dependent on the nature of the support.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Less is more: It is much less efficient to synthesize both components of a multivalent recognition site separately than it is to use one multivalent component to act as a template for the catalytically orchestrated construction of the other component, as demonstrated by the formation of the mechanically interlocked, triply threaded molecular bundle shown. The situation is reiniscent of nature.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Extracurricular laboratory:new discovery of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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An efficient synthetic route to a novel macrocyclic aryl alpha-diimine ligand bearing C6 hydrocarbon bridges connecting the aryl ortho positions is described. Pd(II) and Ni(II) complexes with the new macrocyclic ligand (10 and 14) were successfully synthesized and characterized. The X-ray crystal structures of complexes 10 and 14 show that the complexes exhibit coordination geometry similar to that of their acyclic analogues and the alkyl bridges do not introduce significant ring strain into the complexes. The preactivated Pd(II) complex 12 and the allyl nickel complex 14 were tested for ethylene polymerization. Potential reasons for the low catalytic activities are discussed.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Novel transition metal complexes are provided which represent viable catalysts for a broad variety of reactions such as hydrogenation reactions and metathesis reactions. Novel preparation processes are made available via unprecedented routes inter alia not involving structures according to Grubbs I or Grubbs II catalysts.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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A short route for the synthesis of Pachastrissamine (Jaspine B), an anhydrosphingosine derivative, and all three of its diastereomers is presented. The route consists of only 9 steps from the commercially available Garner’s aldehyde. The furan framework is formed via an eta3-allylpalladium intermediate.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Extracurricular laboratory:new discovery of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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This article describes new selectivities for Grubbs’ first and second generation catalysts when occluded in a hydrophobic matrix of polydimethylsiloxane (PDMS). Occlusion of catalysts in mm-sized slabs of PDMS is accomplished by swelling with methylene chloride then removing the solvent under vacuum. The catalysts are homogenously dissolved in PDMS yet remain catalytically active. Many substrates that react by olefin metathesis with Grubbs’ catalysts freely dissolved in methylene chloride also react by olefin isomerization with occluded catalysts. Eleven examples of substrates that exhibit dual reactivity by undergoing olefin isomerization with occluded catalysts and olefin metathesis with catalysts dissolved in methylene chloride are reported. Most of these substrates have olefins with allylic phosphine oxides, carbonyls, or ethers. Control experiments demonstrate that isomerization is occurring in the solvent by decomposition of the catalyst from a ruthenium carbene to a proposed ruthenium hydride. This work was extended by heating occluded Grubbs’ first generation catalyst to 100 C in 90% MeOH in H2O in the presence of various alkenes to transform the Grubbs’ catalyst into an isomerization catalyst for unfunctionalized olefins. This work demonstrates that occlusion of organometallic catalysts in PDMS has important implications for their reactions and can be used as a method to control which reactions they catalyze.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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(Chemical Equation Presented) A radical change: Implementation of a radical-mediated rearrangement of the bicyclo[3.2.1]octyl moiety to the bicyclo-[2.2.2]octane structure has enabled a concise synthesis of the tricyclic core of platencin, a newly discovered antibiotic. An intramolecular aldol and a ring-closing metathesis reaction were subsequently used to complete the synthesis of the tricycle (see scheme).

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI