Sep 2021 News The Absolute Best Science Experiment for Tetrapropylammonium perruthenate

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The first total synthesis of violaceoid A, a cytotoxic agent, and the asymmetric total synthesis of (-)- and (+)-violaceoid B are reported. The precursor was accessed by desymmetrization of a substituted quinol moiety, and the racemic secondary alcohol was kinetically resolved using a chiral nucleophilic catalyst. The asymmetric synthesis of (-)- and (+)-violaceoid B elucidated the absolute configuration of the naturally occurring violaceoid B. Synthetic violaceoid A inhibited the growth of human breast cancer cell lines MCF-7 and Hs 578T at concentrations of less than 100 muM, while (S)- and (R)-violaceoid B were inactive.

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

Sep 2021 News Properties and Exciting Facts About Dichloro(benzene)ruthenium(II) dimer

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Chemistry is an experimental science, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 37366-09-9, Name is Dichloro(benzene)ruthenium(II) dimer, COA of Formula: C12H12Cl4Ru2.

The invention belongs to the field of anti-tumor research, discloses a double-nuclear […] complex preparation method and its in the topoisomerase inhibiting and application in treating tumor. […] complexes of the present invention the cationic part of the structure shown in formula I of. The invention optimizes the binuclear […] complex preparation process, the raw material cost is low, the reaction time is short. The resulting complex has high purity, has good water-solubility and excellent spectral properties. The invention binuclear […] complex has very high DNA is inserted into the combining ability, thus having extremely high topoisomerase inhibitory activity, and better anti-tumor effect, one of the complex-induced human prostate cancer cell 22 Rv1 late apoptosis of capacity than cisplatin, is a very application the value of potential anti-tumor medicament. (by machine translation)

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

Sep 2021 News Archives for Chemistry Experiments of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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The cyano complexes (eta5-C5H5)M(Ph2PCH2CH2PPh2)CN (4, M = Fe; 6, M = Ru) and (eta5-C5H5)Ru(PPh3)2CN (5) have been prepared by treatment of the corresponding chlorides with methanolic potassium cyanide.The nucleophilicity of the cyano ligand has been demonstrated by the reactions of 5 with a variety of mild electrophiles (MeI, EtI, allyl bromide, PhCH2Br, ICH2CH2OH and cyclohexene oxide) to form the corresponding isonitrile cations.

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

Sep 2021 News Extracurricular laboratory:new discovery of Dichloro(benzene)ruthenium(II) dimer

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Condensation of (R)-2-aminobutanol with salicylaldehyde and 2-pyrrolecarbaldehyde gave the chiral chelate ligands HLL1* and HLL2*, respectively. The diastereomeric complexes (RRu,RC)- and (SRu,RC)-[(eta6-arene)Ru(LL 1*)Cl], eta6-arene = p-cymene (1a/1b), eta6-arene = benzene (2a/2b)1 and (RRu,RC)- and (SRu,RC)[(eta6-arene)Ru(LL 2*)Cl], eta6-arena = p-cymene (3a/3b), eta6-arene = benzene (4a/4b), which only differ in the ruthenium configuration, were prepared by the reaction of [(eta6-arene)RuCl2]2 with the anion of the corresponding ligand HLL*. X-ray analyses of 1a/1b and 3a/ 3b showed a structural peculiarity. The unit cell of these complexes contained diastereomers with the same configuration at the carbon atoms but opposite configuration at the metal centers in a 1:1 ratio. Weak intramolecular O-H…Cl hydrogen bridges were formed in all the complexes. 1H-NMR studies demonstrated the configurational lability at the Ru center. The iodo complexes (RRu,RC)- and (SRu,RC)-[(eta6-p-cymene)Ru(LL*)I], LL* = LL1* (5a/5b) and LL* = LL2* (6a/6b), were synthesized by halogen exchange.

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

6-Sep-2021 News Extracurricular laboratory:new discovery of (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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Cyclase enzymes weave simple polyprenyl chains into the elaborate polycyclic ring systems of terpenes, a sequence that is often difficult to emulate under abiotic conditions. Here we report a disparate synthetic approach to complex terpenes whereby simple prenyl-derived chains are cyclized using radical, rather than cationic, reaction pathways. This strategy allowed us to efficiently forge the intricate 5-8-5 fused ring systems found in numerous complex natural product classes and also enabled a nine-step total synthesis of (-)-6-epi-ophiobolin N, a member of the large family of cytotoxic ophiobolin sesterterpenes. A small-molecule thiol catalyst was found to override the inherent diastereoselectivity observed during a reductive radical cascade cyclization process. This work lays the foundation for efficient synthesis of terpenoid ring systems of interest in medicinal research, particularly those that have been historically challenging to access.

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

6-Sep-2021 News Awesome and Easy Science Experiments about Ruthenium(III) chloride

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GdIII-containing metallostar contrast agents are gaining increased attention, because their architecture allows for a slower tumbling rate, which, in turn, results in larger relaxivities. So far, these metallostars find possible applications as blood pool contrast agents. In this work, the first example of a tissue-selective metallostar contrast agent is described. This RGD-peptide decorated RuII(GdIII) 3metallostar is synthesized as an alphavbeta 3-integrin specific contrast agent, with possible applications in the detection of atherosclerotic plaques and tumor angiogenesis. The contrast agent showed a relaxivity of 9.65 s-1 mM-1, which represents an increase of 170%, compared to a low-molecular-weight analogue, because of a decreased tumbling rate (tauR = 470 ps). The presence of the MLCT band (absorption 375-500 nm, emission 525-850 nm) of the central Ru II(Ph-Phen)3-based complex grants the metallostar attractive luminescent properties. The 3MLCT emission is characterized by a quantum yield of 4.69% and a lifetime of 804 ns, which makes it an interesting candidate for time-gated luminescence imaging. The potential application as a selective MRI contrast agent for alphavbeta 3-integrin expressing tissues is shown by an in vitro relaxometric analysis, as well as an in vitroT1-weighted MR image.

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

6-Sep-2021 News The important role of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 246047-72-3, Recommanded Product: 246047-72-3

A practical and highly enantio- (up to 94:6 er) and diastereoselective (up to >20:1 dr) synthesis of I-butenolides bearing two adjacent stereogenic centers is reported featuring a sequential direct palladium-catalyzed asymmetric allylic alkylation/(E)-selective cross-metathesis/[3,3]-sigmatropic Cope rearrangement from readily available alpha-substituted (5H)-furan-2-ones.

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

6-Sep-2021 News Extended knowledge of Dichlorodicarbonylbis(triphenylphosphine)ruthenium(II)

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14564-35-3, Name is Dichlorodicarbonylbis(triphenylphosphine)ruthenium(II), molecular formula is C38H34Cl2O2P2Ru, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 14564-35-3, Application In Synthesis of Dichlorodicarbonylbis(triphenylphosphine)ruthenium(II)

The “weak-link approach” for the synthesis of metallomacrocycles has been used to synthesize a series of novel Ru(II) macrocycles in high yield. RuCl2(PPh3)3 has been reacted with two different phosphino-alkyl-ether hemilabile ligands, 1,4-(PPh2(CH 2)2O)2C6H4 and 1,4-(PPh2(CH2)2OCH2) 2C6H4. The hemilabile bidentate ligand coordinates to Ru(II) centers through both the P and O atoms to form bimetallic “condensed intermediates”. The weak Ru-O bonds have been selectively cleaved with CO, 1,2-diaminopropane, and pyridine to yield large open macrocycles. This is the first example of the weak-link approach employed to synthesize macrocycles with Ru, and metal centers in general that have more than four coordination sites.

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

6-Sep-2021 News A new application about (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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A recently isolated bismonoglyceride of heptadecanedioic acid, which represents a novel type of natural monoglycerides (i.e., with two instead of only one glycerol unit in the molecular architecture), was synthesized in enantiopure forms using a chiral-pool based approach with the 17-carbon chain constructed from undec-10-enoic acid and oct-7-en-1-ol via a cross metathesis and the stereogenic centers derived from (R)-(2,2-dimethyl-1,3-dioxolan-4-yl) methanol. An analogue with a longer alkyl chain was also synthesized. The synthetic samples not only allowed for establishment of the absolute configuration but also helped to reveal some minor yet unignorable errors in the 1H NMR data for the natural product. Optical rotation and NMR data acquired in DMSO and DMSO-d6, respectively, are also presented.

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

6-Sep-2021 News Some scientific research about (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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Polyketide biosynthetic pathways have been engineered to generate natural product analogs for over two decades. However, manipulation of modular type I polyketide synthases (PKSs) to make unnatural metabolites commonly results in attenuated yields or entirely inactive pathways, and the mechanistic basis for compromised production is rarely elucidated since rate-limiting or inactive domain(s) remain unidentified. Accordingly, we synthesized and assayed a series of modified pikromycin (Pik) pentaketides that mimic early pathway engineering to probe the substrate tolerance of the PikAIII-TE module in vitro. Truncated pentaketides were processed with varying efficiencies to corresponding macrolactones, while pentaketides with epimerized chiral centers were poorly processed by PikAIII-TE and failed to generate 12-membered ring products. Isolation and identification of extended but prematurely offloaded shunt products suggested that the Pik thioesterase (TE) domain has limited substrate flexibility and functions as a gatekeeper in the processing of unnatural substrates. Synthesis of an analogous hexaketide with an epimerized nucleophilic hydroxyl group allowed for direct evaluation of the substrate stereoselectivity of the excised TE domain. The epimerized hexaketide failed to undergo cyclization and was exclusively hydrolyzed, confirming the TE domain as a key catalytic bottleneck. In an accompanying paper, we engineer the standalone Pik thioesterase to yield a thioesterase (TES148C) and module (PikAIII-TES148C) that display gain-of-function processing of substrates with inverted hydroxyl groups.

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