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Activation of olefin metathesis complexes containing unsymmetrical unsaturated N-heterocyclic carbenes by copper and gold transmetalation

The activation of ruthenium-indenylidene complexes containing two unsymmetrical unsaturated N-heterocyclic carbenes (u2-NHCs) by a transmetalation process is reported. The use of copper(i) or gold(i) chlorides promotes the rapid trapping of one NHC ligand, which releases the catalytically active Ru-species. Impressive initiation rates with full-conversions are observed within one minute. This practical protocol demonstrates excellent catalytic performances in various ring-closing metathesis (RCM) and self-metathesis (SM) reactions.

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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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Synthesis of stable ruthenium olefin metathesis catalysts with mixed anionic ligands

A series of ruthenium carboxylate complexes that contain two different anionic ligands was prepared. The complexes that bear iodide ligands exhibit remarkable chemical stability. Such complexes have a diminished tendency to undergo anionic ligand exchange and can be activated byvarious acids to form catalysts, which are active in olefinmetathesis reactions. Ruthenium carboxylate complexes that contain an iodide ligand exhibit remarkable stability. Such complexes can be activated by various acids (HA) to form mixed ligand catalysts 12, which are active in metathesis reactions and possess a diminished tendency for anionic ligand exchange.

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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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Conducting Olefin Metathesis Reactions in Air: Breaking the Paradigm

The first study of low catalyst loading olefin metathesis reactions in air is reported. TON values of up to 7000 were obtained using nondegassed solvents with commercially available precatalysts Caz-1, Hov-II, and Ind-II. The simple experimental conditions allow olefin metathesis reactions to be carried out on the benchtop using technical grade solvents in air. (Chemical Equation Presented).

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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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Kinetic selectivity of olefin metathesis catalysts bearing cyclic (alkyl)(amino)carbenes

The evaluation of ruthenium olefin metathesis catalysts 4-6 bearing cyclic (alkyl)(amino)carbenes (CAACs) in the cross-metathesis of cis-1,4-diacetoxy-2- butene (7) with allylbenzene (8) and the ethenolysis of methyl oleate (11) is reported. Relative to most NHC-substituted complexes, CAAC-substituted catalysts exhibit lower E/Z ratios (3:1 at 70% conversion) in the cross-metathesis of 7 and 8. Additionally, complexes 4-6 demonstrate good selectivity for the formation of terminal olefins versus internal olefins in the ethenolysis of 11. Indeed, complex 6 achieved 35 000 TONs, the highest recorded to date. CAAC-substituted complexes exhibit markedly different kinetic selectivity than most NHC-substituted complexes.

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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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Regio- and Diastereoselective Functionalization of 3-Amino-hexahydrooxazoninones

The regio- and diastereoselectivity of transformations of nine-membered lactams with a Z double bond in the cyclic tether towards building blocks for medicinal chemistry was evaluated. To this end, 3-aminohexahydrooxazoninones were synthesized using a standard ring-closing metathesis (RCM) approach of easily available O,N-bisallylated serine derivatives. The obtained Z double bond in the medium sized lactam was used as a handle to evaluate the stereoselectivity of electrophile induced transformations. It was shown that dibromination and electrophilic activation by NBS followed by attack of O-nucleophiles proceeded in a diastereoselective manner. Cyclization of obtained bromohydrins and face-selective epoxidation gave access to both diastereomers of the epoxidized lactams. Finally, a Heck-reaction of a bromobenzyl moiety at the lactam N-atom with the Z-double bond resulted in the diastereoselective formation of bicyclic bridged nine-membered lactams.

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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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In an article, published in an article, once mentioned the application of 301224-40-8, Name is (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride,molecular formula is C31H38Cl2N2ORu, is a conventional compound. this article was the specific content is as follows.HPLC of Formula: C31H38Cl2N2ORu

Asymmetric synthesis of (+)-polyanthellin A

(Chemical Equation Presented) A concise and convergent route to (+)-polyanthellin A is presented. This synthesis features a diastereoselective cyclopropane/aldehyde [3+2] cycloaddition to install the hydroisobenzofuran core. The use of MADNTf2 as a potent, bulky Lewis acid was essential to allow a labile beta-silyloxy aldehyde to be used in the cycloaddition. Other key steps include a ring-closing metathesis and a selective olefin oxidation.

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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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Synthetic studies on Stemona alkaloids. Construction of the sessilifoliamides B and C and 1,12-secostenine skeleton

An original synthetic approach to the Stemona alkaloids stenine and sessilifoliamides B and C has been explored. The strategy relies on the early construction of the pyrroloazepine core (rings A and B) and latter addition of the furanone (ring D) and ethyl chain at C-10, which are the common structural features of the three alkaloids. The formation of the azabicyclic nucleus through an intramolecular Morita-Baylis-Hillman reaction of a properly substituted pyrrolidone has been extensively investigated by modifications on the substrate and all the parameters involved in the process and an efficient protocol in terms of yield and stereoselectivity has been developed. Despite many alternative tactics were explored, insurmountable difficulties found in the last synthetic steps have frustrated the completion of the syntheses. However, along the way, a plethora of new compounds was prepared, some of them containing the full skeleton of the targeted alkaloids, which can be useful for future synthetic applications.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Application In Synthesis of (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride. 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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Ruthenium olefin metathesis catalysts bearing an N-fluorophenyl-N-mesityl- substituted unsymmetrical N-heterocyclic carbene

Two new ruthenium-based olefin metathesis catalysts, each bearing an unsymmetrical N-heterocyclic carbene ligand, have been synthesized and fully characterized. Their catalytic performance has been evaluated in ring-closing metathesis, cross metathesis, and ring-opening metathesis polymerization reactions.

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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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Synthesis of benzaldehyde-functionalized LewisX trisaccharide analogs for glyco-SAM formation

LewisX (Lex) antigen based carbohydrate-carbohydrate interactions are mediated by complexation of metal ions. Although theoretical studies about the influence of participating hydroxyl groups in the Le x trisaccharide head group (Galbeta(1-4)[Fucalpha(1-3)]GlcNAc) could gave same rudimental information about the basic mechanism behind this interaction, a little is known about orientation and configuration of the hydroxyl groups required for the specific interaction mediated by Ca 2+ complexation. Therefore, there is a need of non-natural derivatives to provide detailed information about the requirements for hydroxyl group arrangement in Lex head group surface plasmon resonance and gold nanoparticle techniques have shown to be powerful tools to investigate carbohydrate-carbohydrate interactions. Benzaldehyde-functionalized glycans can be used for attachment to both gold nanoparticles and surface plasmon resonance sensor surfaces. Therefore, seven benzaldehyde equipped Lex analogs including the natural trisaccharide were synthesized utilizing convergent approach. The derivatives were applied in ongoing carbohydrate-carbohydrate interaction studies by surface plasmon resonance experiments to prove theoretical postulate about the structural requirements of hydroxyl group arrangements in Lex trisaccharides.

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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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Enantioselective synthesis of planar-chiral ferrocene-fused 4-pyridones and their application in construction of pyridine-based organocatalyst library

A couple of planar-chiral ferrocene-fused 4-pyridone derivatives 2a and 2b were synthesized in enantiomerically pure form by scalable asymmetric transformations. Pyridones 2 are versatile precursors to various ferrocene-fused pyridine derivatives, which are useful nucleophilic asymmetric organocatalysts.

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