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Ladder-shaped polyether (LSP) toxins represented by brevetoxins and Ciguatoxins are thought to bind to transmembrane (TM) proteins. To elucidate the interactions of LSPs with TM proteins, we have synthesized artificial ladder-shaped polyethers (ALPs) containing 6/7/6/6 tetracyclic, 6/7/6/6/7/6/6 heptacyclic, and 6/7/6/6/7/6/6/7/6/6 decacyclic systems, based on the convergent method via alpha-cyano ethers. The ALPs possessing the simple iterative structure with different numbers of rings would be useful for structure-activity relationship studies on the molecular length, which is supposed to be important when naturally occurring LSPs elicit their toxicity. Two series of ALPs were prepared to evaluate the hydrophilic or hydrophobic effects of the side chains: (i) both sides were functionalized as diols (A series), and (ii) one side remained as diol and the other side was protected as benzyl ethers (B series). To examine the interaction of these ALPs with TM proteins, dissociation of glycophorin A (GpA) dimers into monomers was evaluated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The heptacyclic ether (ALP7B) elicited the most potent activity in the presence of 2% SDS buffer, whereas the decacyclic ether (ALP10A) exhibited an intriguing phenomenon to induce precipitation of GpA in a dose-dependent manner, under the low concentration of SDS (0.03%). ALP10A also induced precipitation of integrin alpha 1beta1, a TM protein known to form heterodimers in the lipid bilayer membranes. The different activities among the ALPs can be accounted for by the concept of “hydrophobic matching” that is, lengths of the hydrophobic region including the side chains of ALP7B and ALP10A are ca. 25 A, which match the lengths of the hydrophobic region of alpha-helical TM proteins, as well as the hydrophobic thickness of lipid bilayer membranes. The concept of the hydrophobic matching would be a clue to understanding the interaction between LSPs and TM proteins, and also a guiding principle to design ALPs possessing potent affinities with TM proteins.

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

Archives for Chemistry Experiments of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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A general method for carbocyclization of carbohydrates is described using two consecutive organometallic transformations: a novel zinc-mediated domino reaction to give functionalized dienes followed by ring-closing olefin metathesis. In the first reaction, methyl omega-deoxy-omega-iodo glycosides undergo reductive elimination with zinc to produce a terminal double bond. This also liberates the aldehyde which is immediately alkylated in situ by various organozinc reagents. The alkylation occurs under Barbier conditions with methylene iodide and several allyl bromides. Zinc plays a dual role by both promoting the reductive elimination and activating the alkyl halide. Vinylation is carried out by adding divinylzinc. When a new stereogenic center is generated, moderate to excellent stereocontrol is generally observed. An amino group can be introduced by trapping the intermediate aldehyde as an imine prior to the alkylation. The reductive elimination-allylation sequence can also be promoted by indium metal. All the alkylations produce a second double bond, and the obtained dienes are subsequently subjected to ring-closing olefin metathesis to produce the corresponding carbocycles. Newly developed catalyst 30 with an N-heterocyclic carbene ligand is more reactive toward these carbohydrate-derived dienes than commercially available catalyst 18. Acetylation of the free hydroxy groups improves the metathesis reaction significantly. Both five- and six-membered carbocycles are available by this route, including a number of conduritols and quercitols.

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

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu. In a Article,once mentioned of 246047-72-3, Safety of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

Commercially available catalysts (SIMes)(PCy3)Cl 2Ru(CHPh) (2) and (SIMes)Cl2Ru(CH-o-O-i-PrC 6H4) (3) (SIMes = 1,3-dimesitylimidazolin-2-ylidene) were found to display reversible Ru oxidations via a series of electrochemical measurements. The redox processes enabled the catalysts to be switched between two different states of activity in ring opening metathesis polymerizations and ring closing metathesis reactions, primarily through changes in catalyst solubility. Moreover, treating a solution of 2 dissolved in C6H 6/CH2Cl2/[1-butyl-3-methylimidazolium][PF 6] (6:1:1.1 v/v/v) with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was found to remove >99.9% of the catalyst, as determined by UV/vis spectroscopy. The methodology described herein establishes a new approach for controlling the activities displayed by commercially available olefin metathesis catalysts and for removing residual Ru species using redox-driven processes.

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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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We have developed a simple and an efficient route to a range of angularly fused spirocycles by the application of enyne metathesis and the Diels-Alder reaction as key steps. The enyne metathesis protocol has been further extended to the dibenzylation of indane-1,3-dione by using cross-enyne metathesis in the presence of hexa-1,5-diene with the aid of Grubbs’ 1st generation catalyst followed by an aromatization sequence with DDQ.

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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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Deprotonation of a simple borylated allylic sulfone and subsequent alkylation with certain unsaturated electrophiles provide substrates that are easily converted into functionalized alkenyl boronates with ring sizes from five- to seven-membered. A Chan-Lam reaction on one such substrate afforded an alkoxyallylic sulfone that was readily converted via a (4 + 3)-cycloaddition to a polycycle possessing the ABC ring substructure of ingenol.

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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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The reactant in an enzyme-catalyzed reaction is called a substrate. Enzyme inhibitors cause a decrease in the reaction rate of an enzyme-catalyzed reaction.I hope my blog about 246047-72-3 is helpful to your research., COA of Formula: C46H65Cl2N2PRu

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Abstract The activity and selectivity of silica-supported Hoveyda-Grubbs (HG) complex for the cross-metathesis of methyl oleate with 1-hexene to obtain 1-decene, methyl 9-tetradecenoate, 5-tetradecene and methyl 9-decenoate were studied in a batch reactor. The HG complex loading was varied between 0.87 and 11.6 wt%. Competitive secondary reactions were the self-metathesis of methyl oleate and the self-metathesis of 1-hexene. The yield to cross-metathesis products (etaC-M) was 47% when a 1-hexene/methyl oleate reactant ratio (RC6/MO) of one was employed. The etaC-M value increased with increasing 1-hexene initial concentration, reaching 87% for RC6/MO = 7. The selectivity to terminal olefins also increased at the expense of internal olefins among the cross-metathesis products when the concentration of 1-hexene was increased.

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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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Density functional theory calculations are reported concerning the dissociative mechanism for alkene metathesis by ruthenium dichloride catalysts, including both bisphosphine and diaminocarbene/phosphine complexes. The calculations use a hierarchy of models, ranging from [(L)(PH3)Ru(Cl) 2(CH2)] (L = PH3 or diaminocarbene) through the larger [(L)(PMe3)Ru(Cl)2(CHPh)] to the “real” [(L)(PCy3)Ru(Cl)2(CHPh)]. Calculations show that the rate-limiting step for metathesis is either ring closing from an alkene complex to form a ruthena-cyclobutane, or ring-opening of the latter intermediate to form an isomeric alkene complex. The higher efficiency of the diaminocarbene based catalysts is due to the stabilization of the formal +IV oxidation state of the ruthenium centre in the metallacycle. This effect is partly masked in the smaller model systems due to a previously unnoticed stereoelectronic effect. The calculations do not reproduce the experimental observation whereby the initiation step, phosphine dissociation, is more energetically demanding and hence slower for the diaminocarbene-containing catalyst system than for the bisphosphine. Further calculations on the corresponding bond energies using a variety of DFT and hybrid DFT/molecular mechanics methods all find instead a larger phosphine dissociation energy for the bisphosphine catalyst. This reversed order of binding energies would in fact be the one expected based on the stronger trans influence of the diaminocarbene ligand. The discrepancy with experiment is small and could have a number of causes which are discussed here. The Royal Society of Chemistry 2005.

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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 flexible protocol for the synthesis of three lipophilic alpha-amino acid components of some novel cyclic peptides having important histone deacetylase inhibiting properties has been developed from a common source, which featured a cross-metathesis reaction between two unhindered terminal olefins as the key step.

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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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Unsaturated spirocyclic substrates bearing two alkenyl chains underwent ruthenium-mediated ring-rearrangement metathesis through relaying cyclohexene and cycloheptene moieties to give angularly fused tricyclics. In some instances where two products were expected, high degrees of selectivity were observed. In one instance the structural parameter leading to selectivity was very subtle; in others the transformation favoured the formation of products with a cis-fused cyclohexene moiety. An unusual transformation involving ring-opening, double-bond migration, and then ring-closing was observed.

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

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A new protocol based on sequential applications of three atom-economic processes viz. Claisen rearrangement, olefin isomerisation, and ring-closing diene metathesis has been developed to access a range of linear and angularly fused pyranocoumarin derivatives. Incorporation of enyne (in place of diene) metathesis and Diels-Alder reaction in the sequence has allowed the corresponding benzannulated derivatives to be prepared in good yields.

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