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Olefin metathesis catalysts

The present invention refers to novel ruthenium- and osmium-based catalysts for olefin metathesis reactions, particularly to catalysts having stereoselective properties. Z-selectivity is obtained by utilizing two mono-anionic ligands of very different steric requirement. In olefin metathesis reactions these catalysts selectively provide the Z-isomer of disubstituted olefinic products.

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

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Total synthesis and cytotoxic activity of dechlorogreensporones A and D

The first and convergent total syntheses of polyketide natural products dechlorogreensporones A and D have been accomplished in 17 longest linear steps with 2.8% and 5.4% overall yields, respectively, starting from known methyl 2-(2-formyl-3,5-dihydroxyphenyl)acetate and commercially available R-(+)-propylene oxide and 1,2-epoxy-5-hexene. Our synthesis exploited key Mitsunobu esterification and (E)-selective ring-closing metathesis (RCM) to assemble the macrocycles as well as a Jacobsen hydrolytic kinetic resolution to install the stereogenic centers. Both synthetic compounds were found to display significant cytotoxic activity against seven human cancer cell lines with the IC50 ranges of 6.66?17.25 muM.

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

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Total synthesis of platensimycin and related natural products

Platensimycin is the flagship member of a new and growing class of antibiotics with promising antibacterial properties against drug-resistant bacteria. The total syntheses of platensimycin and its congeners, platensimycins B1 and B3, platensic acid, methyl platensinoate, platensimide A, homoplatensimide A, and homoplatensimide A methyl ester, are described. The convergent strategy developed toward these target molecules involved construction of their cage-like core followed by attachment of the various side chains through amide bond formation. In addition to a racemic synthesis, two asymmetric routes to the core structure are described: one exploiting a rhodium-catalyzed asymmetric cycloisomerization, and another employing a hypervalent iodine-mediated de-aromatizing cyclization of an enantiopure substrate. The final two bonds of the core structure were forged through a samarium diiodide-mediated ketyl radical cyclization and an acid-catalyzed etherification. The rhodium-catalyzed asymmetric reaction involving a terminal acetylene was developed as a general method for the asymmetric cycloisomerization of terminal enynes.

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

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Total synthesis of (-)-isoschizogamine

A first asymmetric total synthesis of (-)-isoschizogamine has been accomplished. Our synthesis features the facile construction of the carbon framework of the natural product through a Wagner-Meerwein rearrangement, a tandem metathesis, a stereoselective rhodium-mediated 1,4-addition of an arylboronic acid, and a ring-closing metathesis via a hemiaminal ether.

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

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Divergent reactivity of alk-5-ynylidenecyclopropanes in the presence of the 1st or the 2nd generation Grubbs’ catalysts

Alk-5-ynylidenecyclopropanes, by virtue of being equipped with a strained cyclopropane system, can be divergently elaborated into bicyclo[3.3.0]octenes or exocyclopropylidenecycloalkenes depending on whether they react with the first or the second generation Grubbs’ ruthenium carbenes. While the highly reactive second generation system catalyses the formation of ring-closing metathesis products, the less [metathesis] active first generation carbene promotes an intramolecular [3 + 2] cycloaddition to give the bicarbocyclic skeletons.

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

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RUTHENIUM POLYMERISATION CATALYSTS

Cis and trans ruthenium complexes that can be used as catalysts for ring opening metathesis polymerisation (ROMP) are described. The complexes are generally square pyramidal in nature, having two anionic ligands X. Corresponding cationic complexes where one or both of the anionic ligands X are replaced by a non-co-ordinating anionic ligand are also described. Polymers such as polydicyclopentadiene (PDCPD) can be prepared using the catalysts.

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

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Ionically tagged ru-alkylidenes for metathesis reactions under biphasic liquid-liquid conditions

The synthesis of the novel ionic Ru-alkylidenes [Ru[(4-CO2)(1-CH3)Py+)]2(IMesH2)(=CH-2-(2-PrO)-C6H4)][OTf-]2 (1, IMesH2=1,3-dimesitylimidazolin-2-ylidene, Py=pyridine, OTf-=triflate) and [RuCl[(4-CO2)(1-CH3)Py+)](IMesH2)(=CH-2-(2-PrO)-C6H4)][OTf-] (2) is reported. Catalysts 1 and 2 were successfully used in various metathesis reactions under biphasic liquid-liquid conditions using 1-butyl-2,3-dimethylimidazolium tetrafluoroborate and heptane as liquid phases. Ruthenium leaching into the heptane phase was very low (<0.4%), translating into Ru contamination of the products between 0.3 and 2.5ppm. Both 1 and 2 exhibited comparable reactivity in organic solvents and under biphasic conditions. Catalyst 1 and 2 were also successfully used in the continuous metathesis of methyl oleate and 1,7-octadiene under supported liquid-liquid conditions. Finally, the disproportionation of the monocarboxylato monochloro substituted Ru-alkylidene 2 was traced by 1HNMR analysis at 40C, thereby demonstrating the formation of complex 1 and the neutral complex [RuCl2(IMesH2)(=CH-2-(2-PrO)-C6H4)]. Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.COA of Formula: C31H38Cl2N2ORu. In my other articles, you can also check out more blogs about 301224-40-8

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

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.301224-40-8, Name is (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride, molecular formula is C31H38Cl2N2ORu. In a Article£¬once mentioned of 301224-40-8, Product Details of 301224-40-8

Ionic-tagged catalytic systems applied to the ethenolysis of methyl oleate

A novel high selective ionophilic Hoveyda-type complex for the methyl oleate ethenolysis was prepared from Grubbs first generation catalyst. Ethenolysis under classical biphasic systems in ionic liquids showed to be mass-transference limited. This drawback was successfully solved by the catalyst dispersion on high specific surface area inorganic supports through a thin layer of ionic liquids (ILs). The supported ionic liquid phase (SILP) catalyst properties were patterned by the support type, IL cation and support/IL mass ratio. The SILP prepared with the IL 1-isopentyl-3-methylimidazole hexafluorophosphate and silica showed a turnover number higher (up to 2350) than that of biphasic systems (up to 1045).

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

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Expeditious synthesis of the cores of naturally occurring cyclic polyethers using a divergent ring rearrangement metathesis strategy

Ring rearrangement metathesis (RRM) strategies are proposed for the expeditious synthesis of the cores of naturally occurring cyclic polyethers of the dysiherbaine and acetogenin families, as well as a hybrid compound, from 8-oxabicyclo[3.2.1]octenes. Copyright

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

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Lewis-acid assisted cross metathesis of acrylonitrile with functionalized olefins catalyzed by phosphine-free ruthenium carbene complex

The exchange of the PPh3 ligand in the complex [1,3-bis(2,6-dimethylphenyl)4,5-dihydroimidazol-2-ylidene](PPh 3)-(Cl)2Ru=CHPh (7) for a pyridine ligand at ambient temperature leads to the formation of the stable phosphine-free carbene ruthenium complex [1,3-bis(2,6-dimethylphenyl)4,5-dihydroimidazol-2-ylidene] (C5H5N)2(Cl)2 Ru=CHPh (8). The resulted ruthenium complex exhibits highly catalytic activity for the cross metathesis of acrylonitrile with various functionalized olefins under mild conditions, and its activity can be further improved by the addition of a Lewis acid such as Ti(O?Pr)4. In the mixture products, the Z-isomer predominates. The Royal Society of Chemistry 2005.

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