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Synthesis of functionalized cyclic boronates

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

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Cyclotrimerization of alkynes and isocyanates/isothiocyanates catalyzed by ruthenium-alkylidene complexes

Ruthenium carbene catalysts are able to catalyze crossed [2+2+2] cyclotrimerizations of alpha,omega-diynes with isocyanates, isothiocyanates, and carbon disulfide. Both aliphatic and aromatic isocyanates can be used to produce fused 2-pyridones, although aliphatic isocyanates were more reactive. Aromatic isocyanates give better results when they bear electron-donating substituents. The reaction of unsymmetrical alpha,omega-diynes gave a product only with the substituent adjacent to the 2-pyridone nitrogen. Isothiocyanates gave thiopyranimines upon reaction with the C-S bond, whereas CS2 reacted efficiently to give a thioxothiopyrane.

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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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Iterative asymmetric allylic substitutions: Syn- and anti-1,2-diols through catalyst control

A copper-catalyzed asymmetric allylic boronation (AAB) gives access to syn- and anti-1,2-diols. The method facilitates an iterative strategy for the preparation of polyols (see scheme), such as the fully differentiated L-ribo-tetrol and protected D-arabino-tetrol. P=protecting group Copyright

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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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Total Synthesis of Solandelactones A and B

The total synthesis of solandelactones A and B is presented. The eastern cyclopropyl moiety was prepared following an exceptionally short chemoenzymatic approach whereas enantioselective synthesis of the western side-chain relied on the application of diastereomerically pure allyl boronates. The natural products solandelactones A and B were isolated in good overall yields following convergence of each eastern and western element by application of the Nozaki-Hiyama-Kishi reaction.

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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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A Novel Jaspine B-Ceramide Hybrid Modulates Sphingolipid Metabolism

A new sphingolipid hybrid molecule was designed to assemble, within a tail-to-tail double-chain structure, the ceramide hydrophilic moiety and the tetrahydrofuran pharmacophore of jaspine B, a natural product known to interfere with sphingolipid metabolism. This compound was prepared through acylation of sphingosine with a jaspine B derivative bearing a COOH group in the terminal position of the aliphatic backbone. This new hybrid molecule was evaluated for its capacities to affect melanoma cell viability and sphingolipid metabolism. While retaining the cytotoxicity of ceramide itself, this compound was shown to lower the sphingomyelin cellular levels and significantly enhance the production of sphingosine-1-phosphate, thus representing a novel sphingolipid metabolism modulator.

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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 highly stable 1,3-diaryl-1 H -1,2,3-triazol-5-ylidenes and their applications in ruthenium-catalyzed olefin metathesis

The formal cycloaddition between 1,3-diaza-2-azoniaallene salts and alkynes or alkyne equivalents provides an efficient synthesis of 1,3-diaryl-1H-1,2,3- triazolium salts, the direct precursors of 1,2,3-triazol-5-ylidenes. These N,N-diarylated mesoionic carbenes (MICs) exhibit enhanced stability in comparison to their alkylated counterparts. Experimental and computational results confirm that these MICs act as strongly electron-donating ligands. Their increased stability allows for the preparation of ruthenium olefin metathesis catalysts that are efficient in both ring-opening and ring-closing 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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Z – And enantioselective ring-opening/cross-metathesis with enol ethers catalyzed by stereogenic-at-Ru carbenes: Reactivity, selectivity, and Curtin-Hammett kinetics

The first instances of Z- and enantioselective Ru-catalyzed olefin metathesis are presented. Ring-opening/cross-metathesis (ROCM) reactions of oxabicyclic alkenes and enol ethers and a phenyl vinyl sulfide are promoted by 0.5-5.0 mol % of enantiomerically pure stereogenic-at-Ru complexes with an aryloxy chelate tethered to the N-heterocyclic carbene. Products are formed efficiently and with exceptional enantioselectivity (>98:2 enantiomer ratio). Surprisingly, the enantioselective ROCM reactions proceed with high Z selectivity (up to 98% Z). Moreover, reactions proceed with the opposite sense of enantioselectivity versus aryl olefins, which afford E isomers exclusively. Preliminary DFT calculations in support of Curtin-Hammett kinetics as well as initial models that account for the stereoselectivity levels and trends are provided.

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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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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.301224-40-8, Name is (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride, molecular formula is C31H38Cl2N2ORu. In a Article£¬once mentioned of 301224-40-8, Computed Properties of C31H38Cl2N2ORu

Ring-Closing Enyne Metathesis of Terminal Alkynes with Propargylic Hindrance

The ring closing enyne metathesis of substrates with propargylic hindrance was investigated, revealing the successful combination of the Stewart-Grubbs catalysts and microwave heating sometimes up to 170 C for oxacycles. Medium-sized rings were obtained from terminal alkynes previously reputed as reluctant substrates. This unmatched combination was applied to the synthesis of carbocycles and oxacycles. In addition, this is the first report on the use of the Stewart Grubbs catalyst in ring closing enyne metatheses. (Figure 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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A short and efficient total synthesis of ficuseptamines A and B

A rapid and efficient total synthesis of ficuseptamines A and B by a cross metathesis strategy is described.

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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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Cross metathesis of several methylenecyclopentane derivatives

The cross metathesis (CM) of several methylenecyclopentane derivatives using Hoveyda-Grubbs second generation catalyst 4 (5-10 mol %) has been studied. Medium to good yields of tetrasubstituted alkenes have been obtained. In the case of 8-methyl-2,5-dimethylene-2,3,5,6-tetrahydro-1H,4H-3a,6a- (methanoiminomethano)pentalene-7,9-dione 2 products from single, double and triple CM were formed. With 8-methyl-5-methylene-5,6-dihydro-3a,6a- (methanoiminomethano)pentalene-2,7,9(1H,3H,4H)-trione 3 a good yield of the CM product was obtained working at 140C in xylene for 3 d, showing the high thermal stability of this catalyst. In the CM of diene 2 and enone 3, the main products were always the anti-stereoisomers.

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