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SYNTHESIS OF OLEFINIC ALCOHOLS VIA ENZYMATIC TERMINAL HYDROXYLATION

In certain aspects, the present invention provides methods for producing terminally hydroxylated alkenes and alkynes by contacting an unsaturated or saturated hydrocarbon substrate with a hydroxylase enzyme. Exemplary terminal hydroxylases useful for carrying out the methods of the invention exhibit strong selectivity towards one terminal carbon of a hydrocarbon substrate and include, but are not limited to, non-heme diiron alkane monooxygenases, cytochromes P450 (e.g., cytochromes P450 of the CYP52 and CYP153 family), as well as long chain alkane hydroxylases. In some embodiments, the terminally hydroxylated alkene or alkyne is further converted to a terminal alkenal. In certain embodiments, terminally hydroxylated alkenes and alkynes are useful as insect pheromones which modify insect behavior. In other embodiments, terminally hydroxylated alkenes and alkynes are useful intermediates for producing pheromones via acetylation or oxidation of the alcohol moiety.

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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 new route to vitamin E Key-intermediates by olefin cross-metathesis

Ru-Catalyzed olefin cross-metathesis (CM) has been successfully applied to the synthesis of several phytyl derivatives (2b, 2d-f, 3b) with a trisubstituted C=C bond, as useful intermediates for an alternative route to alpha-tocopheryl acetate (vitamin E acetate; 1b) (Scheme 1). Using the second-generation Grubbs catalyst RuCl2(C21H 26N2)(CHPh)PCy3, (Cy = cyclohexyl; 4a) and Hoveyda-Grubbs catalyst RuCl2(C21H26N 2){CH-C6H4(O-iPr)-2} (4b), the reactions were performed with various C-allyl (5a-f, 7a,b) and O-allyl (8a-d) derivatives of trimethylhydroquinone-1-acetate as substrates. 2,6,10,14-Tetramethylpentadec-1-ene (6a) and derivatives 6c-e of phytol (6b) as well as phytal (6f) were employed as olefin partners for the CM reactions (Schemes 2 and 5). The vitamin E precursors could be prepared in up to 83% isolated yield as (E/Z)-mixtures.

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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, Application In Synthesis of (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

Ring opening-cross metathesis of unstrained cycloalkenes

Unstrained cycloalkenes undergo ruthenium-catalysed ring opening-cross metathesis reactions with simple alpha,beta-unsaturated carbonyl compounds under mild conditions.

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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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Asymmetric total syntheses of xanthatin and 11,13-dihydroxanthatin using a stereocontrolled conjugate allylation to gamma-butenolide

The stereocontrolled conjugate allylation to an optically pure gamma-butenolide provided direct and reliable access to a trans-fused series of xanthanolide sesquiterpenoids and allowed for the enantioselective total syntheses of xanthatin and 11,13-dihydroxanthatin to be efficiently achieved.

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

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Ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelating and preparation method and application thereof (by machine translation)

The invention provides a ruthenium carbene olefin metathesis catalyst containing bidentate sulfur ligand chelating and a structural, formula thereof. The olefin metathesis catalyst prepared by the method disclosed, by the invention, has excellent catalytic activity and three-dimensional selectivity and high structural stability, and the olefin metathesis, catalyst has the ROMP advantages, of high yield and relatively good selectivity Z -and is high in yield and selectivity. (by machine translation)

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

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Factors relevant for the regioselective cyclopolymerization of 1,6-heptadiynes, N,N-dipropargylamines, N,N-dipropargylammonium salts, and dipropargyl ethers by RuIV-alkylidene-based metathesis initiators

The factors relevant for the regioselectivity of insertion of various 1,6-heptadiynes, N,N- dipropargylamines, N,N-dipropargylammonium salts anddipropargyl ethers into different RuIV-alkylidenes, i.e., [R u(CF 3COO)2(IMesH2)(=CHR), (R = 2,4,5-(MeO) 3-C6H2(l1) 2-(2-PrO)-5-NO2-C 6H3 (I3), 2-(2- PrO)-C6H4 (I4)), [Ru(CF3COO)2(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2- ylidene)(=CH-2-(2-PrO)-5- NO2-C6H3)] (I2), [Ru(CF3COO)2(3-mesityl-1-((1?fl)-1?- phenylethyl)-imidazolin-2-ylidene)(=CH-2-(2-PrO)- C6H4)] (I5) and [Ru(C6F5COO)2(IMesH 2)(=CH-2-(2-PrO)-C6H4)] (I6), (IMesH 2 = 1,3-dimesitylimidazolin-2- ylidene), is described. 13C NMR experiments revealed that all polymers synthesized by the action of I1-I6 consisted virtually solely (>95percent) of five-membered repeat units, i.e., (cyclopent-1-enylene)-1,2-vinylenes, 3,4-(1 H-2,5-dihydropyrrylenium)-3,4- vinylenes, and (2-pentyl-2,5-dihydrofurylene)-3,4-vinylenes, respectively. The 13C NMR-based assignments were supported by the synthesis of model compounds, i.e., (cyclopent- 3-ene-1,1-diyldimethylbis(tris(3,5-dimethoxyphenyl) carboxylate) (MC1) and N-propyl-N-ethyl-2,5-dihydro- pyrrolium tetrafluoroborate (MC2), as well as by ene-yne cross metathesis reactions of 3-(propargyloxy)- 1-octyne (M6) with trimethylallylsilane. In the polymerization of N-ethyl-N,N-dipropargylamine (M9), an intermediate was isolated that shedslight onto the role of heteroatoms in the 4-position of 1,6-heptadiynes in cyclopolymerization. In addition, in the cyclopolymerization of M9 b y I4 the product resulting from backbiting has been isolated and explains for the low polymerization propensity of Ru-alkylidenes for N-alkyl-N,N-dipropargylamines.

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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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Ammonium-tagged ruthenium-based catalysts for olefin metathesis in aqueous media under ultrasound and microwave irradiation

The influence of microwave and ultrasonic irradiation on the performance of ammonium-tagged Ru-based catalysts in olefin metathesis transformations in aqueous media was studied. Differences in the catalytic activity in correlation with the nature of the present counter ion and the size of the N-heterocyclic carbene (NHC) ligand were revealed. The presented methodology allows for preparation of a variety of polar and non-polar metathesis products under environmentally friendly conditions.

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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 alpha,beta-unsaturated aldehydes and nitriles via cross-metathesis reactions using Grubbs’ catalysts

A series of alpha,beta-unsaturated aldehydes and nitriles of significant interest in the fragrance industry have been prepared using Grubbs’ catalysts in cross-metathesis reactions of electron-deficient olefins (i.e., acrolein, crotonaldehyde, methacrolein, and acrylonitrile) with various 1-alkenes, including 1-decene, 1-octene, 1-hexene and 2-allyloxy-6-methylheptane. The latter is of particular interest, as it has not previously being used as a substrate in cross-metathesis reactions and allows access to valuable intermediates for the synthesis of new fragrances. Most reactions gave good selectivity of the desired CM product (?90%). Detailed optimisation and mechanistic studies have been performed on the cross-metathesis of acrolein with 1-decene. Recycling of the catalyst has been attempted using ionic liquids.

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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, category: ruthenium-catalysts

Cationic ruthenium alkylidene catalysts bearing phosphine ligands

The discovery of highly active catalysts and the success of ionic liquid immobilized systems have accelerated attention to a new class of cationic metathesis catalysts. We herein report the facile syntheses of cationic ruthenium catalysts bearing bulky phosphine ligands. Simple ligand exchange using silver(i) salts of non-coordinating or weakly coordinating anions provided either PPh3 or chelating Ph2P(CH2)nPPh2 (n = 2 or 3) ligated cationic catalysts. The structures of these newly reported catalysts feature unique geometries caused by ligation of the bulky phosphine ligands. Their activities and selectivities in standard metathesis reactions were also investigated. These cationic ruthenium alkylidene catalysts reported here showed moderate activity and very similar stereoselectivity when compared to the second generation ruthenium dichloride catalyst in ring-closing metathesis, cross metathesis, and ring-opening metathesis polymerization assays.

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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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Enyne ring-closing metathesis on heteroaromatic cations

Cationic heteroaromatic enynes have been employed as substrates in enyne ring-closing metathesis, under an atmosphere of ethylene and using the Hoveyda-Grubbs catalyst, for the first time; the reaction affords new 1-vinyl- and 2-vinyl-substituted 3,4-dihydroquinolizinium salts, useful precursors for biologically relevant cations based on the quinolinizium system. The Royal Society of Chemistry 2006.

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