17-Sep-21 News Discovery of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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(Chemical Equation Presented) Lock it in: A temporary silicon-based configurational lock (see scheme) has enabled an efficient and fully diastereo-selective assembly of the spiroketal subunit of spirofungin A. This complex natural product was synthesized in 20 steps, including a rapid polyketide assembly based on the ring-opening metathesis of a cyclopropenone acetal. It was established that spirofungin A elicited notable anti-proliferative activity against several human cancer cell lines and selectively inhibited isoleucyl-tRNA synthetase in vitro.

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

09/16/21 News Top Picks: new discover of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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The synthesis of small organic molecules as probes for discovering new therapeutic agents has been an important aspect of chemical-biology. Herein we report a reagent-based, diversity-oriented synthetic (DOS) strategy to probe chemical and biological space via a “Click, Click, Cyclize” protocol. In this DOS approach, three sulfonamide linchpins underwent cyclization protocols with a variety of reagents to yield a collection of structurally diverse S-heterocycles. In silico analysis is utilized to evaluate the diversity of the compound collection against chemical space (PC analysis), shape space (PMI) and polar surface area (PSA) calculations.

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

16-Sep-21 News Some scientific research about (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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The synthesis of novel sulfur-chelated ruthenium benzylidenes afforded latent catalysts with a wider range of activities and new isomeric forms. A ruthenium complex with a tridentate ligand displayed latency for even one of the most reactive ROMP monomers, dicyclopentadiene, while a room temperature latent trifluoromethyl-substituted thioether derivative was shown to be the most active sulfur-chelated precatalyst to date in several metathesis reactions at higher temperatures. These new complexes widen the spectrum of activity for this family of catalysts, enabling several practical applications and enhancing the understanding for the mechanisms of activation in strongly chelated ruthenium alkylidenes.

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

9/16/21 News Awesome and Easy Science Experiments about (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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Both (3R,5S)- and (3R,5R)-gingerdiols were synthesized. Their 1,3-diol motifs were derived from enantiopure epoxy chiral building blocks that were readily accessible from D-gluconolactone. The effect of deuterating the OH groups of the natural isomer on its optical rotation was also examined. In the course of the syntheses of the targets, an unexplored cross-metathesis (CM) reaction of unprotected 5-substituted pent-1-ene-3,5-diols was investigated, in which the CM product readily underwent an allylic epimerization and oxidation, as the starting diols rearranged into ketones with unprecedented ease. These problems were eventually resolved by performing the CM reaction in toluene in the presence of phenol. The cause of these unexpected, yet very interesting phenomena, was determined to be the presence of the unprotected OH group at C-5 of the 5-substituted pent-1-ene-3,5-diol. A mechanistic rationale is also presented. Copyright

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

9/16/21 News Top Picks: new discover of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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The synthesis and characterization of monomeric and dendritic Grubbs II and Hoveyda-Grubbs II-based complexes are reported. These complexes were synthesized via a route based on the connection of monomeric or dendritic N-alkyl-N?-mesitylimidazol-2-ylidene pre-ligands to Grubbs I or Hoveyda-Grubbs I complexes. The immobilization of a modified Grubbs II type catalyst on a G0 carbosilane dendrimer was successfully carried out. Together with monomeric Grubbs II and Hoveyda-Grubbs-analogs and several commercially available olefin metathesis catalysts, the soluble, homogeneous G0-dendritic Grubbs II complex was tested as catalyst in the ring closing metathesis of diethyl diallylmalonate. The immobilized complex proved to outperform its monomeric analog in this reaction at room temperature, whereas it was found to be slightly slower at reflux temperature.

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

9/15/21 News A new application about (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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(Chemical Presented) Wormholes through chemical space: Spirocyclic oxetanes are described as analogues of morpholine and also as topological siblings of their carbonyl counterparts. They are particularly promising in terms of both their physicochemical properties and the ease with which they can be grafted onto molecular structures. The data collected highlight oxetanes as both the hydrophilic sister of a gem-dimethyl unit and the carbonyl group’s lipophilic brother.

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

9/15 News Awesome and Easy Science Experiments about (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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(?)-Isoguaiene was prepared from (S)-citronellal in only 9?10 steps with good overall yields. Either a trienyne or a dienediyne metathesis and highly diastereoselective organocatalytic Michael additions of aldehydes derived from (S)-citronellal served as the key transformations.

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

15-Sep-21 News The important role of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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Cross metathesis (CM) reactions of methyl oleate (MO) with cis-4-octene (OC), cis-stilbene (CS) using RuCl2(PCy3)(IMesH2)(CHPh) [IMesH2 = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene; Cy = cyclohexyl] afforded CM products with high MO conversion and high selectivity under high molar (OC/MO, CS/MO) ratios; CM with cis-1,4-diacetoxy-2-butene also afforded metathesis products with high MO conversion under certain conditions. The efficient CM with allyltrimethylsilane proceeded with high activity, whereas the CM with glycidyl ether, beta-pinene, and vanillylidenacetone proceeded with low MO conversion.

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

15-Sep-21 News Archives for Chemistry Experiments of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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Ring-opening metathesis (ROM) of various unsaturated, constrained bicyclic ring systems has been investigated with the use of commercial ruthenium-based catalysts. Starting from various cyclodienes, the corresponding derived bicyclic lactone, lactam, and isoxazoline derivatives were submitted to ROM under ethenolysis. These functionalized, strained bicyclic systems afforded novel highly-functionalized diolefinated heterocyclic scaffolds in ROM reactions with stereocontrol, through the conservation of the configuration of the stereogenic centers of the starting compounds.

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

14/9/2021 News The Absolute Best Science Experiment for (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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A tandem cross metathesis (CM)-ring-closing metathesis (RCM) sequence to form cyclic siloxanes is reported. This new enyne metathesis platform expands the scope and utility of the regio- and stereoselective cross metathesis reaction between silylated alkynes and terminal alkenes. The initial cross metathesis was directed to occur on the alkyne by employing sterically hindered mono-, di-, and trisubstituted alkenes tethered to the alkyne via silyl ether. The regio- and stereoselectivity feature of the initial CM step in this tandem CM-RCM process is identical to that of the CM reactions of silylated alkynes and alkenes. This tandem sequence provides both synthetically useful silylated 1,3-diene building blocks and insights into the reaction mechanism of the enyne metathesis reaction.

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