Discovery of (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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The first catalytic, broadly applicable, efficient, gamma-, diastereo-, and enantioselective method for addition of O-substituted allyl-B(pin) compounds to phosphinoylimines (MEM=methoxyethoxymethyl, pin=pinacolato) is presented. The identity of the most effective catalyst and the optimal protecting group for the organoboron reagent were determined by consideration of the steric and electronic requirements at different stages of the catalytic cycle, namely, the generation of the chiral allylboronate, the subsequent 1,3-borotropic shift, and the addition step. Aryl-, heteroaryl-, alkenyl- and alkyl-substituted vicinal phosphinoylamido MEM-ethers were thus accessed in 57?92 % yield, 89:11 to >98:2 gamma:alpha selectivity, 76:24?97:3 diastereomeric ratio, and 90:10?99:1 enantiomeric ratio. The method is scalable, and the phosphinoyl and MEM groups may be removed selectively or simultaneously. Utility is highlighted by enantioselective synthesis of an NK-1 receptor antagonist.

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

Discovery of (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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The first catalytic, broadly applicable, efficient, gamma-, diastereo-, and enantioselective method for addition of O-substituted allyl-B(pin) compounds to phosphinoylimines (MEM=methoxyethoxymethyl, pin=pinacolato) is presented. The identity of the most effective catalyst and the optimal protecting group for the organoboron reagent were determined by consideration of the steric and electronic requirements at different stages of the catalytic cycle, namely, the generation of the chiral allylboronate, the subsequent 1,3-borotropic shift, and the addition step. Aryl-, heteroaryl-, alkenyl- and alkyl-substituted vicinal phosphinoylamido MEM-ethers were thus accessed in 57?92 % yield, 89:11 to >98:2 gamma:alpha selectivity, 76:24?97:3 diastereomeric ratio, and 90:10?99:1 enantiomeric ratio. The method is scalable, and the phosphinoyl and MEM groups may be removed selectively or simultaneously. Utility is highlighted by enantioselective synthesis of an NK-1 receptor antagonist.

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

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New generations of Hoveyda and bis-carbene type of ruthenium-based olefin metathesis catalysts (10 and 12), containing cationic cyclic alkyl amino carbene (CAAC) ligands, have been synthetized. The catalysts show exceptional stability and activity in environmentally benign, protic media. Various olefin metatheses reactions of OH functionalized feedstock (e. g. RCM, ROMP CM) can be carried out at as low as 0.05 mol % catalyst loading in methanol, isopropanol, water or methanol/water solvent mixture, accomplishing the lowest applied catalyst loading reported so far in these media. The facile olefin metathesis of renewable feedstocks including phospholipids (23) and vegetable oils (20) in protic media has also been demonstrated.

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

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Infections caused by Mycobacterium tuberculosis kill more than 1.8 million people each year. While the persistence of this pathogenic bacterial species and the emergence of multidrug resistant strains have created an urgent need for new TB therapies, a new TB-specific drug has not been developed in over 40 years. The disclosure herein provides short and scalable syntheses of small molecules, and small molecules as new therapeutics for eradicating this life threatening pathogen.

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

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Diketo-1,3-dioxin-2-ones underwent retro-Diels-Alder reaction on heating in toluene at 110C to generate alpha,gamma,epsilon-triketo-ketenes. These were trapped with alcohols to provide 2,4,6-triketocarboxylates, which were smoothly aromatized by sequential reaction with potassium carbonate and methanolic hydrogen chloride to give resorcylate esters. The reaction was applied in the total synthesis of the marine antifungal agents 15G256beta (1), 15G256iota (2), and 15G256pi (3) and the mycotoxin S-(-)-zearalenone (4).

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

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A norbornene-functionalized derivative of acetylacetone has been used to synthesize a series of new polymerizable norbornene-derivatized phosphorescent platinum complexes of the form Pt(C?N)(O?O*) where C?N represents a cyclometalated ligand and O?O* represents the functionalized acetylacetonate ligand. The complexes have been fully characterized, and the structures of three examples have been determined by X-ray diffraction. Solution absorption and luminescence spectra and electrochemical data are very similar to those for analogues without these polymerizable groups. A 9,9-dialkyl-2,7-di(carbazol-9-yl)fluorene material, in which one of the alkyl groups bears a norbornene group, has been synthesized and copolymerized with the Pt(C?N)(O?O*) complexes using Grubbs ruthenium catalysts, resulting in copolymers with broad molecular weight distributions. The copolymers have been used as lumophores in organic light-emitting diodes, thus demonstrating that platinum phosphors can be successfully integrated into the “hybrid” approach to organic light-emitting diodes, in which molecules with transport or luminescent properties are covalently attached to electronically inert polymer backbones to give solution-processible materials. Emission from aggregate states appears to play a similar role in these copolymers to that seen in vapor-deposited devices based on small phosphor and host molecules; in particular, considerable aggregate emission is observed when a phosphor with blue solution emission is used in the devices.

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

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Aromatic fluorinated hydrocarbons, used as solvents for olefin metathesis reactions, catalysed by standard commercially available Ru precatalysts, allow substantially higher yields to be obtained, especially of challenging substrates, including natural and biologically active compounds. The Royal Society of Chemistry 2008.

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

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A series of ruthenium catalysts has been screened in the self-metathesis of 1-dodecene with and without the addition of benzoquinones. Many of these catalysts demonstrated excellent selectivity and yields with as low as 10 ppm catalyst loading. Reactions have been conducted under decreased pressure or under argon bubbling, which caused a tremendous increase in yield and selectivity of the examined process. Copyright

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

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Ruthenium-alkylidene-catalyzed cross-metathesis of a range of homologous alkenylamine salts provides expedient and high-yielding routes to commercially valuable polyamide monomers using a single catalyst, telescopic workup, and mild experimental conditions.

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

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The multijet oscillating disk (MJOD) flow reactor is a relatively new technology for continuous flow synthesis. This technology is still under investigation as an all-round platform for flow synthesis. In this article, findings are disclosed from a project where a MJOD flow reactor rig (reactor volume of ?50 mL) was investigated as the reaction platform for ring closing metathesis and cross (self) metathesis reaction, using reaction mixture volumes down to only ?5 mL. The Hoveyda-Grubbs second-generation catalyst was used without an inert atmosphere. The results of the flow synthesis provided excellent selectivity and high yield. For comparison purposes, the syntheses conducted in the MJOD reactor were compared with similar literature experiments performed with other flow technologies and batch conditions.

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