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A new synthetic route to optically active unsaturated gamma- and delta-lactones has been demonstrated via asymmetric allylic carboxylation with a planar-chiral Cp?Ru catalyst and ring-closing metathesis reaction with a Grubbs II catalyst, and successfully applied to the enantioselective synthesis of (R)-(-)-massoialactone. The Royal Society of Chemistry 2012.

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

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

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Concise asymmetric total syntheses of the fungal metabolites (-)-stephacidin A, (+)-stephacidin B, and (+)-notoamide B are described. Key features of these total syntheses include (1) a facile synthesis of (R)-allyl proline methyl ester, (2) a revised route toward the pyranoindole ring system, (3) a novel cross-metathesis strategy for the introduction of important functional groups, and (4) an SN2? cyclization to form the [2.2.2] bridged bicyclic ring system. Furthermore, our synthesis has taken advantage of microwave heating to shorten reaction times as well as increase yields for the preparation of vital intermediates.

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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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Two novel ruthenium-based olefin metathesis catalysts, H 2ITap(PCy3)Cl2Ru=CH-Ph 12 and H 2ITapCl2Ru=CH-(C6H4-O-iPr) 13 (H2ITap = 1,3-bis(2?,6?-dimethyl-4?- dimethylaminophenyl)-4,5-dihydroimidazol-2-ylidene), were synthesized bearing a pH-responsive NHC ligand with two aromatic NMe2 groups. The crystal structures of complexes 12 and 13 were determined via X-ray crystallography. Both catalysts perform ring opening metathesis polymerization (ROMP) of cyclooctene (COE) at faster rates than their commercially available counterparts H2IMes(PCy3)Cl2Ru=CH-Ph 2 and H 2IMesCl2Ru=CH-(C6H4-O-iPr) 3 (H 2IMes = 1,3-bis(2?,4?,6?-trimethylphenyl)-4,5- dihydroimidazol-2-ylidene) and perform at similar rates during ring closing metathesis (RCM) of diethyldiallylmalonate (DEDAM). Upon addition of 2 equiv. of HCl, catalyst 12 is converted into a mixture of several mono and diprotonated Ru-carbene species 12? which are soluble in methanol but degrade within a few hours at room temperature. Catalyst 13 can be protonated with 2 equiv. of HCl and the resulting complex 13? is moderately water-soluble. The complex is stable in aqueous solution in air for >4 h, but over prolonged periods of time shows degradation in acidic media due to hydrolysis of the NHC-Ru bond. Catalysts 12 and 13 perform RCM of diallylmalonic acid in acidic protic media with only moderate activity at 50 C and do not produce polymer in the ROMP of cationic 7-oxanorbornene derivative 14 under the same conditions. Catalyst 13 was used for Ru-seperation studies when RCM of DEDAM or 3,3-diallypentadione (DAP) was conducted in low-polar organic solution and the Ru-species was subsequently precipitated by addition of strong acid. The Ru-species were removed by (1) filtration and (2) filtration and subsequent extraction with water. The residual Ru-levels could be reduced to as far as 11 ppm (method 2) and 24 ppm (method 1) without the use of chromatography or other scavenging methods.

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

New explortion of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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The synthesis of (+)-mesembrine (1) and (+)-mesembranol (2) has been achieved from the monoterpene (S)-(-)-perillyl alcohol. Key transformations include a diastereo- and regioselective Pd-mediated intramolecular Heck reaction, and a double reduction of the resultant cyclic sulfonamide, to afford the cis-3a-aryloctahydroindole skeleton.

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

Extended knowledge of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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Shape-persistent arylenevinylene macrocycles (AVMs) were successfully prepared in one step from readily available aromatic diene monomers through olefin metathesis in good yields. 1H NMR, UV-Vis absorption and fluorescence studies revealed the aggregation behavior of the obtained macrocycles. SEM characterization showed AVM nanofibril formation.

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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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Ruthenium-indenylidene complexes represent a class of robust and efficient pre-catalysts for olefin metathesis reactions. In this feature article, we provide an overview of the various complexes belonging to this family and summarise their use in various applications. The relation between the nature of ancillary ligands around the metal coordination sphere of these complexes and their catalytic activity is also discussed. The Royal Society of Chemistry.

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

Can You Really Do Chemisty Experiments About (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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The (3S,5R) and (3R,5R) isomers of the title compound were synthesized from enantiopure epoxide chiral building blocks readily accessible from D-gluconolactone. The former (a syn-1,3-diol) gave 1H and 13C NMR spectroscopic data and optical rotation in good agreement with those reported for the natural product, whereas distinct differences were found with the data for the latter (an anti-1,3-diol). These results unambiguously showed that the absolute configuration of the natural product must be (3S,5R).

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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-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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Metathesis condensation and isomerization reactions of allylic compounds were examined using Grubbs’ second-generation ruthenium catalyst [Ru*]. Allyl alcohol and allyl cyanide undergo metathesis condensation releasing ethylene, with conversions being the highest reported for these substrates. However, competing olefin isomerization rather than metathesis can occur under certain conditions when heteroatoms are present at the allylic position to the olefin.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.name: (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium. In my other articles, you can also check out more blogs about 246047-72-3

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

Awesome Chemistry Experiments For (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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The polyhydroxylated beta-amino acids (2S,3R,4S,5S,7E)-3-amino-8-phenyl- 2,4,5-trihydroxyoct-7-enoic acid (APTO) and (2S,3R,4S,5S,7E,9E)-3-amino-10-(4- ethoxyphenyl)-2,4,5-trihydroxydeca-7,9-dienoic acid (AETD) are key components of the microsclerodermin family of anti-fungal cyclic peptides. They have been synthesised in protected form in twelve steps using a unified strategy, with the introduction of the unsaturated sidechain in the final step of the synthesis from a common aldehyde intermediate. The synthesis features the ordered application of asymmetric aminohydroxylation and dihydroxylation reactions to efficiently introduce the stereochemistry of the targets with high selectivity. The Royal Society of Chemistry.

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

Can You Really Do Chemisty Experiments About (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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Despite their simple structures, synthesis of 1(or 3)-acyl-sn-glycerols remains a challenge that cannot be ignored because of facile acyl migrations, which not only complicate the synthesis but also make direct GC or HPLC analysis unfeasible. Assessment of the optical purity of monoacylglycerols has, to date, relied almost exclusively on specific rotation data, which are small in value and thus insensitive to impurities. Now, a simple means to “magnify” the small specific rotations has been found, along with practical methods for the measurement of both 1,2-and 1,3-acyl migrations, which offer a convenient and straightforward alternative to Mori’s NMR analysis of Mosher esters. With the aid of these methods, a range of conditions for deacetonide removal were examined en route to the synthesis of two natural monoacylglycerols. Refined hydrolysis conditions, along with useful knowledge about the solubility and reactivity of substrates with an ultra long alkyl chain are also presented. Copyright

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