111-13-7Relevant articles and documents
Selective ruthenium-catalyzed oxidation of 1,2:4,5-di-O-isopropylidene-β-D-fructopyranose and other alcohols with NaOCl
Gonsalvi, Luca,Arends, Isabel W. C. E.,Sheldon, Roger A.
, p. 1659 - 1661 (2002)
Matrix presented The asymmetric epoxidation catalyst 1,2:4,5-di-O-isopropylidene-β-D-erythro-2,3-hexadiulo-2,6-pyranose 2 was obtained in high yield from 1,2:4,5-di-O-isopropylidene-β-D-fructopyranose 1 via a recyclable ruthenium-catalyzed hypochlorite oxidation protocol under biphasic conditions (MTBE/water) in the presence of an alkaline buffer (pH 9.5). Other secondary alcohols were also oxidized selectively to the correspondinq ketones.
Engineering of P450pyr hydroxylase for the highly regio- and enantioselective subterminal hydroxylation of alkanes
Yang, Yi,Liu, Ji,Li, Zhi
, p. 3120 - 3124 (2014)
Terminal-selective cytochrome P450pyr has been successfully engineered through directed evolution for the subterminal hydroxylation of alkanes with excellent regio- and enantioselectivity. A sensitive colorimetric high-throughput screening (HTS) assay was developed for the measurement of both the regioselectivity and the enantioselectivity of a hydroxylation reaction. By using the HTS assay and iterative saturation mutagenesis, sextuple-mutant P450pyrSM1 was created for the hydroxylation of n-octane (1) to give (S)-2-octanol (2) with 98 % ee and >99 % subterminal selectivity. The engineered P450 is the first enzyme for this type of highly selective alkane hydroxylation, being useful for the Ci-H activation and functionalization of alkanes and the preparation of enantiopure alcohols. Molecular modeling provided structure-based understanding of the fully altered regioselectivity and the excellent enantioselectivity. Another sextuple-mutant P450pyrSM2 catalyzed the hydroxylation of propylbenzene (3) to afford (S)-1-phenyl-2-propanol (4) with 95 % ee and 98 % subterminal selectivity. Get a handle on it: Highly regio- and enantioselective subterminal hydroxylation of n-octane and propylbenzene was observed with P450 enzymes obtained by the directed evolution of terminal-selective P450pyr hydroxylase (see scheme). The engineered enzymes with their fully altered selectivities are useful for the functionalization of alkanes and the preparation of enantiomerically pure alcohols.
A novel heteropolyanion-based amino-containing cross-linked ionic copolymer catalyst for epoxidation of alkenes with H2O2
Leng, Yan,Zhang, Weijie,Wang, Jun,Jiang, Pingping
, p. 306 - 311 (2012)
A heteropolyanion-based cross-linked ionic copolymer was prepared by the anion-exchange of a newly task-specific designed amino-containing ionic copolymer with a Keggin heteropolyacid, and characterized by FT-IR, SEM, TG, XRD, UV-vis, ESR, 1H NMR, and elemental analysis. Its catalytic activity was evaluated in the epoxidation of alkenes with aqueous H 2O2. The resultant heteropolyanion-based ionic copolymer is revealed to be a highly efficient heterogeneous catalyst for epoxidation of alkenes with H2O2, adding the advantages of convenient recovery and steady reuse.
Microstructured Au/Ni-fiber catalyst for low-temperature gas-phase selective oxidation of alcohols
Zhao, Guofeng,Hu, Huanyun,Deng, Miaomiao,Lu, Yong
, p. 9642 - 9644 (2011)
Galvanic deposition of Au onto a thin-sheet sinter-locked 8 μm Ni-fiber delivers a high-performance Au/Ni-fiber catalyst for alcohol oxidation, due to the unique combination of excellent heat conductivity, remarkable low-temperature activity, and good stability/regenerability. The special NiO@Au ensembles formed during the reaction contribute to promoting the low-temperature activity. The Royal Society of Chemistry 2011.
New Cleavable Surfactants Derived from Glucono-1,5-Lactone
Kida, Toshiyuki,Morishima, Nobuaki,Masuyama, Araki,Nakatsuji, Yohji
, p. 705 - 710 (1994)
New amido nonionic cleavable surfactants were synthesized in good yields by the acetalization of glucono-1,5-lactone with octanal, 2-octanone or 2-undecanone, followed by amidation with monoethanolamine, diethanolamine or morpholine.These compounds possessed good water solubilities.The compounds derived from 2-octanone showed higher critical micelle concentrations than the compounds from octanal.For the same hydrophobic chain, both the micelle-forming property and the ability to lower surface tension increased with the change in the terminal amide group in the orderdiethanolamide morpholide monoethanolamide.Interestingly, in spite of their relatively short hydrophobic chains, these compounds showed greater ability to lower surface tension than conventional nonionic surfactants, such as alcohol ethoxylates.Furthermore, their acid-decomposition properties were determined.Their decomposition rates were also compared with that of the corresponding carboxylate type of compound derived from glucono-1,5-lactone. KEY WORDS: Acid-decomposition properties, cleavable surfactant, glucono-1,5-lactone, sugar-derived surfactant, surface-active properties.
Evaluation of tuned phosphorus cavitands on catalytic cross-dimerization of terminal alkynes
Endo, Naoki,Kanaura, Mao,Schramm, Michael P.,Iwasawa, Tetsuo
, p. 4754 - 4757 (2016)
Synthesis of four new bis-phosphorus cavitands is described, including a description of their catalytic use on cross-dimerization of terminal alkynes. The commercially available P[N(CH2CH3)2]3, PhP[N(CH2CH3)2]2, P(OCH3)3, and in situ generated P(NMeBn)3were reacted with a tetra-ol cavitand platform to provide new phosphorus ligands. These ligands readily formed bis-Au complexes that were examined to generate a reactivity profile for the catalytic cross-dimerization of terminal alkynes. We found that the ligand derived from P[N(CH3)2]3gave best product selectivity.
Application of hydrogen peroxide encapsulated in silica xerogels to oxidation reactions
Bednarz, Szczepan,Rys, Barbara,Bogda, Dariusz
, p. 8068 - 8078 (2012)
Hydrogen peroxide was encapsulated into a silica xerogel matrix by the sol-gel technique. The composite was tested as an oxidizing agent both under conventional and microwave conditions in a few model reactions: Noyori′s method of octanal and 2-octanol oxidation and cycloctene epoxidation in a 1,1,1-trifluoroethanol/Na2WO4 system. The results were compared with yields obtained for reactions with 30% H2O2 and urea-hydrogen peroxide (UHP) as oxidizing agents. It was found that the composite has activity similar to 30% H2O2 and has a several advantages over UHP such as the fact that silica and H2O are the only products of the composite decomposition or no contamination by urea or its derivatives occurs; the xerogel is easier to heated by microwave irradiation than UHP and could be used as both an oxidizing agent and as solid support for microwave assisted solvent-free oxidations.
Fe(III) halides as effective catalysts in carbon-carbon bond formation: Synthesis of 1,5-dihalo-1,4-dienes, αβ-unsaturated ketones, and cyclic ethers
Miranda, Pedro O.,Diaz, David D.,Padron, Juan I.,Ramirez, Miguel A.,Martin, Victor S.
, p. 57 - 62 (2005)
(Chemical Equation Presented). Iron(III) halides have proven to be excellent catalysts in the coupling of acetylenes and aldehydes. When terminal acetylenes were used the main products obtained were 1,5-dihalo-1,4-dienes with (E,Z)-stereochemistry contaminated in some cases with (E)-α,β- unsaturated ketones. The former carbonyl derivatives were the sole products isolated when nonterminal aromatic alkynes were used. When homopropargylic alcohols were used, a Prins-type cyclization occurred yielding 2-alkyl-4-halo-5,6-dihydro-2H-pyrans. In addition, anhydrous ferric halides are also shown to be excellent catalysts for the standard Prins cyclization with homoallylic alcohols. Isolation of an intermediate acetal, calculations, and alkyne hydration studies provide substantiation of a proposed mechanism.
Hydrophobic, low-loading and alkylated polystyrene-supported sulfonic acid for several organic reactions in water: Remarkable effects of both the polymer structures and loading levels of sulfonic acids
Iimura, Shinya,Manabe, Kei,Kobayashi, Shue
, p. 2416 - 2418 (2003)
The development of hydrophobic, low-loading and alkylated polystyrene-supported sulfonic acid for organic reactions was studied. The effects of both the polymer structures and loading levels of the sulfonic acid catalysts were also discussed. Hydrophobicity of the catalyst was considered as key for efficient catalysis.
Dialkylborane-catalyzed hydroboration of alkynes with 1,3,2-benzodioxaborole in tetrahydrofuran
Arase,Hoshi,Mijin,Nishi
, p. 1957 - 1962 (1995)
Dialkylborane catalyzed hydroboration of alkynes with an equimolar amount of 1,3,2-benzodioxaborole in tetrahydrofuran efficiently to provide 2-alkenyl-1,3,2-benzodioxaborole under mild reaction conditions.
Continuous biphasic enzymatic reduction of aliphatic ketones
Leuchs, Susanne,Nonnen, Thomas,Dechambre, Dominique,Na'Amnieh, Shukralla,Greiner, Lasse
, p. 52 - 59 (2013)
Biphasic reactions offer an attractive alternative for the utilisation of enzymes for conversion of hardly water soluble substrates. Especially, the alcohol dehydrogenase from Lactobacillus brevis was successfully used for the reductive synthesis of enantiopure secondary aliphatic alcohols. With the enzymatic catalyst and the cofactor effectively retained in the reactive aqueous phase, the continuous operation was demonstrated by continuous addition and withdrawal of the non-reactive phase. The four tested substrates 2-heptanone, 2-octanone, 2-nonanone, and 2-decanone showed that the space time yield and turnover numbers (TON) of the enzyme decrease as the availability of the substrate decreases with increasing partition coefficients. Nevertheless, a TONLbADH of up to 478 × 103 could be achieved. Remarkably, the cofactor utilisation turned out to be very high and a TON NADP+ of more than 20 × 103 was easily achievable for both 2-heptanone and 2-octanone by substrate coupled cofactor regeneration with excess of 2-propanol.
Palladium-Catalyzed Oxidation of Terminal Olefins to Methyl Ketones by Hydrogen Peroxide
Roussel, Michel,Mimoun, Hubert
, p. 5387 - 5390 (1980)
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Ganem,B.,Boeckman,R.K.
, p. 917 - 920 (1974)
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Igersheim,Mimoun
, p. 559 (1978)
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HOMOGENEOUS OXIDATION OF 1-OCTENE BY t-BUTYL HYDROPEROXIDE CATALYZED BY RHODIUM(III) SPECIES
Faraj, Mahmoud,Bregeault, Jean-Marie,Martin, Jacques,Martin, Claudine
, p. C23 - C26 (1984)
Chlororhodium(III) complexes catalyze the oxidation of oct-1-ene by t-BuOOH in R1R2CHOH, to yield products of dioxygen oxidation: i.e. the methyl ketone resulting from olefin oxidation, the acetal or ketone formed by solvent cooxidation, and isomerized olefins.
Catalyse par le palladium at la lumiere ultra-violette de l'oxydation d'alcenes par l'oxygene moleculaire
Muzart, Jacques,Pale, Patrick,Pete, Jean-Pierre
, p. 267 - 274 (1988)
The light-promoted oxidation of terminal alkenes by oxygen in the presence of catalytic amounts of palladium(II) complexes led to corresponding α,β-ethylenic carbonyl compounds and methyl ketones; rapid and extensive isomerisation of the starting alkene is observed.The effect of acetone as solvent on the efficiency of these oxidations is discussed.
Cristol et al.
, p. 2512,2514 (1955)
A Very Useful and Efficient Wacker Oxidation of Higher α-Olefins in the Presence of Per(2,6-di-O-methyl)-β-Cyclodextrin
Monflier, Eric,Tilloy, Sebastien,Fremy, Georges,Barbaux, Yolande,Mortreux, Andre
, p. 387 - 388 (1995)
Oxidation of higher α-olefins (C8-C16) in a two phase system with a multicomponent catalytic system, i.e.PdSO4/H9PV6Mo6O40/CuSO4 and per(2,6-di-O-methyl)-β-cyclodextrin gives the corresponding 2-ketones in high yields ( >90 percent)
PHOTOACTIVATION OF ALKENE OXIDATION BY MOLECULAR OXYGEN IN THE PRESENCE OF PALLADIUM
Muzart, Jacques,Pale, Patrick,Pete, Jean-Pierre
, p. 3577 - 3578 (1982)
A catalytic cycle which leads to α-β ethylenic ketones and methyl ketones from terminal alkenes in the presence of palladium trifluoroacetate, oxygen and U.V. light is described.
Reactions of Nitrosonium Tetrafluoroborate in Acetonitrile with Organic Molecules Containing Nonbonding Electrones. Synthesis of Acetamides
Bach, Robert D.,Taaffee, Thomas H.,Rajan, Sundar J.
, p. 165 - 167 (1980)
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Oxidation of Olefins to Aldehydes Using a Palladium-Copper Catalyst
Wenzel, Timothy T.
, p. 862 - 864 (1993)
Wacker-like catalysts using tert-butyl alcohol as the solvent oxidize terminal olefins to give unusually high selectivities for aldehydes and also provide some insight into the role of copper and oxygen in Wacker-like reactions.
Hydration of terminal alkynes to aldehydes in aqueous micellar solutions by ruthenium(II) catalysis; first anti-Markovnikov addition of water to propargylic alcohols
Alvarez, Patricia,Bassetti, Mauro,Gimeno, José,Mancini, Giovanna
, p. 8467 - 8470 (2001)
The hydration of terminal alkynes and of propargylic alcohols to the corresponding aldehyde derivatives is conveniently carried out at 60°C in an aqueous micellar environment, in the presence of 5 mol% of the indenyl ruthenium(II) complex [Ru(η5-C9H7)Cl(PPh3) 2]. Higher yields and improved regioselectivity of aldehyde versus ketone as well as reaction conditions, in particular temperature and catalyst load, are found with respect to a solvent mixture 2-propanol-water, due to the aggregating conditions of the micellar solution. The reactions of the propargylic alcohols indicate the tolerance of the hydroxy functionality by the ruthenium complex.
Facile Palladium-Catalyzed Decarboxylation Reaction of Allylic β-Keto Esters
Tsuji, Jiro,Nisar, Mohammad,Shimizu, Isao
, p. 3416 - 3417 (1985)
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Ackman et al.
, p. 221,234 (1960)
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Uemura et al.
, p. 218 (1976)
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From Deep Eutectic Solvents to Nitrogen-rich Ordered Mesoporous Carbons: A Powerful Host for the Immobilization of Palladium Nanoparticles in the Aerobic Oxidation of Alcohols
Karimi, Babak,Vali, Hojatollah,Zahra Alizadeh, Seyedeh
, (2022/03/15)
The preparation of a nitrogen-rich ordered mesoporous carbon (DNOMC) with three-dimensional cubic structure was established via carbonization of a green, inexpensive and safe deep eutectic solvent consisting of choline chloride salt and D-glucose in the presence of KIT-6 template for the first time. The materials were characterized by TEM, N2 adsorption–desorption analysis, XPS, TGA, CHN, and FT-IR. The DNOMC was shown to be a powerful support for the immobilization of palladium nanoparticles. The Pd@DNOMC catalyst exhibited high activity in the selective aerobic oxidation of various activated and non-activated primary and secondary benzylic as well as linear and cyclic aliphatic alcohols to the corresponding carboxylic acids and ketones in pure water under molecular oxygen. The catalyst system could successfully be reused at least ten times without any significant decrease in either activity or selectivity. It is worth noting that, the hot filtration strongly showed that the catalyst works in a boomerang-type catalyst pathway.
Expanding the Biocatalytic Toolbox with a New Type of ene/yne-Reductase from Cyclocybe aegerita
Karrer, Dominik,Gand, Martin,Rühl, Martin
, p. 2191 - 2199 (2021/02/26)
This study introduces a new type of ene/yne-reductase from Cyclocybe aegerita with a broad substrate scope including aliphatic and aromatic alkenes/alkynes from which aliphatic C8-alkenones, C8-alkenals and aromatic nitroalkenes were the preferred substrates. By comparing alkenes and alkynes, a ~2-fold lower conversion towards alkynes was observed. Furthermore, it could be shown that the alkyne reduction proceeds via a slow reduction of the alkyne to the alkene followed by a rapid reduction to the corresponding alkane. An accumulation of the alkene was not observed. Moreover, a regioselective reduction of the double bond in α,β-position of α,β,γ,δ-unsaturated alkenals took place. This as well as the first biocatalytic reduction of different aliphatic and aromatic alkynes to alkanes underlines the novelty of this biocatalyst. Thus with this study on the new ene-reductase CaeEnR1, a promising substrate scope is disclosed that describes conceivably a broad occurrence of such reactions within the chemical landscape.
Trans(Cl)-2,2′-bipyridinedicarbonyldichlororuthenium(II) complex catalyzed oxidation of olefins, aryl hydrocarbons and alcohols in homogeneous phase
Sharma, Varsha,Pant, Bhawana,Prakash, Deep,Sagar, Priyanka
, (2021/06/28)
Catalytic oxidation of organic substrates has wide applications in chemical industries due to which huge extensive research work is continuously going on throughout the world. Present study reports efficacious use of Trans (Cl)-2,2′-bipyridinedicarbonyldichlororuthenium(II) complex catalyzed oxidation of internal and terminal olefins, aryl hydrocarbons and alcohols. CH2Cl2–C2H5OH (6:4) was suitable solvent system for these oxidation reactions. The normal pressure oxidation reaction has been carried out at 1 ?atm. Pressure of oxygen and at 300C. The high pressure oxidation reaction was done at 4.48 ?× ?103 KNm3 pressure of oxygen and at 600C. No diminished catalytic activity was observed while checking the recyclability of catalyst up to 6–8 catalytic runs. Catalytic activity was also investigated using tert-butyl hydroperoxide as oxidant inspite of di-oxygen. Effect of different parameters on the rate of oxidation was also studied i.e. extra ligand, temperature, solvents, acids and bases. Kinetic studies have been done and on the basis of kinetics, the mechanism is proposed.