Discovery of (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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(Chemical Equation Presented) We describe the first total synthesis of (-)-himandrine, a member of the class II galbulimima alkaloids. Noteworthy features of this chemistry include a diastereoselective Diels-Alder reaction in the rapid synthesis of the tricycle ABC-ring system in an enantiomerically enriched form, the use of a formal [3+3] annulation strategy to secure the CDE-ring system with complete diastereoselection, and successful implementation of our biogenetically inspired oxidative spirocyclization of an advanced intermediate. The successful and direct late-stage formation of the F-ring in the hexacyclic core of himandrine drew on the power of biogenetic considerations and fully utilized the inherent chemistry of a plausible biosynthetic intermediate.

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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-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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Stereospecific [3,3]-sigmatropic rearrangement of O-substituted thiocarbamate derivatives of enantiopure allylic alcohols provides allylic thiocarbamates as single enantiomers. Intramolecular arylation by rearrangement of their allyllithium derivatives provides allylic tertiary thiols. Allylation and ring-closing metathesis gives 2,5-dihydrothiophenes containing sulfur-bearing quaternary centres. This journal is the Partner Organisations 2014.

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

Simple exploration of (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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This invention relates generally to olefin metathesis catalysts, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the use of such compounds in the metathesis of olefins and in the synthesis of related olefin metathesis catalysts. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and in industrial applications such as oil and gas, fine chemicals, and pharmaceuticals.

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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-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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The investigations disclosed offer insight regarding several key features of Ru-based catecholthiolate olefin metathesis catalysts. Factors influencing the facility with which the two anionic ligands undergo exchange and those that affect the rates of catalyst release are elucidated by examination of more than a dozen new complexes. These studies shed light on how different chelating groups can influence Ru-S bond strength and, as a result, the facility of catecholthiolate rotation. The trans influence series ether < ester ? iodide < amine ? thioether ? olefin < isonitrile ? phosphite has been established through X-ray structural analysis and shown to correlate well with the barrier for catecholthiolate rotation (trans effect) determined by variable-temperature NMR experiments and computational studies (DFT). It is found that, apart from electronic factors, chelate geometry has a more notable effect on the rate of catalyst release (five- vs six-membered chelate ring and mono- vs bidentate ligand). Polytopal processes involving pentacoordinate Ru(II) carbene complexes are shown to be distinct from previously reported fluxional events that involve tetracoordinate species and which are capable of causing diminished polymer syndiotacticity. Ru mercaptophenolate complexes have been synthesized and isolated as a single diastereomer (O-C trans to the NHC). This latter set of species promotes representative olefin metathesis reactions readily and gives Z selectivity levels that are higher than those when the corresponding catecholate systems are used, but less so in comparison to catecholthiolate complexes. A rationale for variations in stereoselectivity is presented. The proportionality constant is the rate constant for the particular unimolecular reaction. the reaction rate is directly proportional to the concentration of the reactant. I hope my blog about 301224-40-8 is helpful to your research., Application of 301224-40-8

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

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Ru-catalyzed olefin metathesis has been successfully applied to the synthesis of biscardanol derivatives and cardanol-based porphyrins. Using Hoveyda-Grubbs catalyst (C627), the reactions were performed with various cardanol derivatives (2, 5, 7, and 9) to make novel biscardanol derivatives. With the use of the second-generation Grubbs catalyst (C848) and Ti(OiPr)4, the ring-closing metathesis of cardanol-based porphyrin 11 was carried out to afford cyclic cardanol-based porphyrin derivative 12.

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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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Applicability of 2-methyltetrahydrofuran for olefin metathesis was examined with a set of ruthenium Hoveyda-type second generation catalysts. Influence of temperature was studied and the results were compared with those obtained in classical solvents for metathesis: dichloromethane and toluene.

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

Awesome Chemistry Experiments For (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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The use of the ring-closing enyne metathesis (RCEYM) as a methodology for the synthesis of the azonino[5,4-b]indole system, featuring the tricyclic substructure of the alkaloids cleavamine and quebrachamine, has been explored. Three series of enyne substrates were studied for their compatibility with the RCEYM reaction. In addition to the usual substrates bearing either a terminal or an internal alkyne, for the first time enynes with an alkynyl halide moiety were also considered. Although the metathesis cyclization allowed for assembly of the azoninoindole nucleus in all three series, an effective catalytic cycle was only noted for internal alkyne substrates. On the basis of the experimental results, the “yne-then-ene” pathway seems to be the mechanism at play in these reactions. The use of ring-closing enyne metathesis (RCEYM) as a methodology for the construction of the nine-membered ring of the 2,3,4,7-tetrahydro-1H-azonino[5,4-b]indole system has been explored.

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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-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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Synthesis of novel polyhydroxylated derivatives of decalin is described. The presented methodology consists in a one-pot copper-catalyzed 1,4-addition of vinylmagnesium bromide to sugar-derived cyclohexenone, followed by an aldol reaction with a derivative of but-3-enal. The obtained diene is then subjected to an assisted tandem catalytic sequence: ring-closing metathesis with the subsequent reuse of the Ru-catalyst in the syn-dihydroxylation. The stereochemical outcome of these reactions is 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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Thiolate-coordinated ruthenium alkylidene complexes can give high Z-selectivity and stereoretentivity in olefin metathesis. To investigate their applicability as heterogeneous catalysts, we have successfully developed a methodology to easily immobilize prototype ruthenium alkylidenes onto hybrid mesostructured silica via a thiolate tether. In contrast, the preparation of the corresponding molecular complexes appeared very challenging in solution. These prototype supported complexes contain small thiolates but still, they are slightly more Z-selective than their molecular analogues. These results open the door to more active and selective heterogeneous catalysts by supporting more advanced thiolate Ru-complexes.

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

Discovery of 301224-40-8

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The in situ preparation of highly stereoretentive ruthenium-based metathesis catalysts is reported. This approach completely avoids the isolation of intermediates and air-sensitive catalysts, thus allowing for the rapid access and evaluation of numerous dithiolate Ru catalysts. A procedure was established to perform cross-metathesis reactions without the use of a glovebox, and on a small scale even Schlenk techniques are not required. Consequently, the chemistry displayed in this report is available to every practicing organic chemist and presents a powerful approach for the identification of new stereoretentive catalysts.

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