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Epoxidation Reactions (epoxidation + reaction)
Selected AbstractsChemInform Abstract: Solvent Effect on Sulfur Ylide Mediated Epoxidation Reaction.CHEMINFORM, Issue 13 2008Hee-Yoon Lee Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Novel Conditions for the Julia,Colonna Epoxidation Reaction Providing Efficient Access to Chiral, Nonracemic Epoxides.CHEMINFORM, Issue 40 2004Thomas Geller Abstract For Abstract see ChemInform Abstract in Full Text. [source] Urea-Hydrogen Peroxide/Hexafluoro-2-propanol: An Efficient System for a Catalytic Epoxidation Reaction Without a Metal.CHEMINFORM, Issue 5 2003Julien Legros No abstract is available for this article. [source] ChemInform Abstract: Developments in the Simmons , Smith-Mediated Epoxidation Reaction.CHEMINFORM, Issue 24 2002Varinder K. Aggarwal Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Novel Chiral (Salen)MnIII Complexes Containing a Calix[4]arene Unit as Catalysts for Enantioselective Epoxidation Reactions of (Z)-Aryl AlkenesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 16 2005Maria E. Amato Abstract New asymmetric (salen)MnIII and UO2 complexes containing a calix[4]arene unit in the ligand framework were synthesized. The UO2 complexes were characterized by 1H-, 13C-, 2D TOCSY and T-ROESY NMR spectroscopy. Furthermore, the structure of one UO2 complex was determined by single-crystal X-ray analysis. The data showed that UO2 complexes, which can be considered in first approximation models of the Mn=O oxidant active species, possess a chiral pocket and adopt relevant conformations for the selectivity of the oxygen transfer process. Epoxidation data of model alkenes with the MnIII complexes showed moderate ee values and were not conclusive in indicating that the calix[4]arene unit might be able to influence the selectivity by a molecular recognition mechanism. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Nanoparticle Supported, Magnetically Recoverable Oxodiperoxo Molybdenum Complexes: Efficient Catalysts for Selective Epoxidation ReactionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2009Sankaranarayanapillai Shylesh Abstract Organic-inorganic hybrid heterogeneous nanocatalyst systems were synthesized by covalent anchoring of oxodiperoxomolybdenum complexes [(LL)MoO(O2)2] on silica coated magnetic nanoparticles as an active, magnetically separable epoxidation catalyst. [source] Overcoming Limitation in the Design of Selective Solid Catalysts by Manipulating Shape and Size of Catalytic Particles: Epoxidation Reactions on SilverCHEMCATCHEM, Issue 9 2010Prof. Suljo Linic Shaping up selectivity: Developments in the synthesis of catalytic particles of targeted size and shape might create opportunities for the design of catalysts for the selective heterogeneous production of low-volume, high-value commodity chemicals. Although these advances are encouraging, scale-up issues in the synthesis of exotic nanostructures and their long-term stability under reaction conditions need to be addressed. [source] Sulfonium Ylide Epoxidation Reactions: Methylene Transfer.CHEMINFORM, Issue 35 2004Benjamin R. Bellenie Abstract For Abstract see ChemInform Abstract in Full Text. [source] A mutant of the green alga Dunaliella salina constitutively accumulates zeaxanthin under all growth conditionsBIOTECHNOLOGY & BIOENGINEERING, Issue 1 2003EonSeon Jin Abstract A novel mutant (zea1) of the halotolerant unicellular green alga Dunaliella salina is impaired in the zeaxanthin epoxidation reaction, thereby lacking a number of the ,-branch xanthophylls. HPLC analysis revealed that the zea1 mutant lacks neoxanthin (N), violaxanthin (V) and antheraxanthin (A) but constitutively accumulates zeaxanthin (Z). Under low-light physiological growth conditions, the zea1 (6 mg Z per g dry weight or 8 × 10,16 mol Z/cell) had a substantially higher Z content than the wild type (0.2 mg Z per g dry weight or 0.5 × 10,16 mol Z/cell). Lack of N, V, and A did not affect photosynthesis or growth of the zea1 strain. Biochemical analyses suggested that Z constitutively and quantitatively substitutes for N, V, and A in the zea1 strain. This mutant is discussed in terms of its commercial value and potential utilization by the algal biotechnology industry for the production of zeaxanthin, a high-value bioproduct. © 2002 Wiley Periodicals, Inc. Biotechnol Bioeng 81: 115,124, 2003. [source] Studies on Nickel(II) Complexes with Amide-Based Ligands: Syntheses, Structures, Electrochemistry and Oxidation ChemistryEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2008Jyoti Singh Abstract The present work discusses the nickel chemistry in a set of amide-based open-chain ligands with subtle differences in the backbone or terminal amine substituents. The ligands coordinate to the Ni2+ ion through the Namide and Namine atoms maintaining a square-planar geometry. Absorption spectra and NMR studies reveal that the solid-state square-planar geometry is retained in solution. The electrochemical results suggest that the NiIII/NiII redox couple primarily depends on the N4 donors, which is composed of two Namide and twoNamine atoms and not on the peripheral substituents. All four ligands with variable backbone and substituents are equally competent in stabilizing the NiIII state. On the basis of electrochemical findings, chemical oxidations were carried out, and they reveal generation of the NiIII state in two cases, whereas decomposition was observed in others. Preliminary alkene epoxidation reactions suggest that the present nickel complexes transiently stabilize the higher oxidation state of the nickel ion that possibly participates in the oxidation of the substrates.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Oxidation of ,4 - and ,5 -Steroids with Hydrogen Peroxide Catalyzed by Porphyrin Complexes of MnIII and FeIIIEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 23 2004Susana L. H. Rebelo Abstract In this paper we describe a new environmentally friendly method to promote the stereoselective epoxidation of ,4 - and ,5 -steroids. Metalloporphyrins efficiently catalyze the epoxidation reactions of 17,-acetoxy-4-androstene (1), 4-cholestene (2) and 3,-acetoxy-5-cholestene (3) in the presence of H2O2 as oxygen donor. Modeling the molecular structure of the porphyrin as well as the central metal allows the control of the preferential formation of ,- or ,-epoxides. Porphyrins with bulky, electron-withdrawing groups in the ortho positions of the meso phenyls and with MnIII as the central metal ion, such as [Mn(TDCPP)Cl], gave preferentially the ,-epoxide of ,4 - and ,5 -steroids. [Fe(TPFPP)Cl] catalyzes preferentially the ,-epoxidation of ,4 -steroids and also increases the stereoselectivity for the ,-epoxide in ,5 -steroids, similar to the results obtained with m -CPBA (m -chloroperbenzoic acid) as oxidant. The substrate structure strongly influences the chemoselectivity of the reactions. The X-ray structures of two main products were determined, and two-dimensional NMR techniques allowed the full assignment of 1H and 13C NMR resonances as well as the stereochemistry of these products. A mechanistic proposal involving oxo species for the ,-approach and peroxy species for the ,-approach is proposed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Extended Hartree,Fock theory of chemical reactions.INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 15 2009Abstract Symmetry and broken symmetry (BS) in molecular orbital description of transition structures and intermediates in oxygenation reactions have been revisited to elucidate states correlation diagrams and mechanisms for addition reactions of molecular oxygen and metal-oxo MO (M = Mn(II) and Fe(II)) species to CC double bonds. Relative stabilities between diradical (DR) and perepoxide (PE) intermediates were thoroughly investigated by several BS hybrid DFT (HDFT) methods and BS CCSD(T) method with and without spin projection. It has been found that recovery of spin symmetry, namely eliminating spin contamination error from the BS solutions, is crucial for the elucidation of reasonable state correlation diagrams and energy differences of the key structures in the oxygenation reactions because the singlet-triplet energy gap for molecular oxygen is large (22 kcal/mol). The BS HDFT followed by spin correction reproduced activation barriers for transition structures along both PE and DR reaction pathways by the use of the CASPT2 method. Basis set dependence on the relative stability between PE and DR intermediates were also examined thoroughly. Solvation effect for DR and PE intermediates was further examined with self-consistent reaction field (SCRF) and SCIPCM methods. Both BS HDFT and CASPT2 have concluded that the DR mechanism is favorable for the addition reaction of singlet oxygen to ethylene, supporting our previous conclusions. The BS HDFT with spin correction was concluded to be useful enough for theoretical investigations of mechanisms of oxygenation reactions. Implications of the computational results were discussed in relation to the theoretical framework (four configuration model) for elucidation of possible mechanisms of epoxidation reactions with Fe(IV)O cores in metalloenzymes on the basis of isolobal analogies among O, OO, and Fe(IV)O. Correspondence between magnetic coupling mode and radical pathway in oxygenations with these species was clarified based on the BS MO interaction diagrams, leading to local singlet and triplet diradical mechanisms for epoxidations. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Amine-Catalyzed Asymmetric Epoxidation of ,,,-Unsaturated AldehydesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 7 2007Gui-Ling Zhao Abstract The direct organocatalytic enantioselective epoxidation of ,,,-unsaturated aldehydes with different peroxides is presented. Proline, chiral pyrrolidine derivatives, and amino acid-derived imidazolidinones catalyze the asymmetric epoxidation of ,,,-unsaturated aldehydes. In particular, protected commercially available ,,,-diphenyl- and ,,,-di(,-naphthyl)-2-prolinols catalyze the asymmetric epoxidation reactions of ,,,-unsaturated aldehydes with high diastereo- and enantioselectivities to furnish the corresponding 2-epoxy aldehydes in high yield with up to 97:3 dr and 98,% ee. The use of non-toxic catalysts, water and hydrogen peroxide, urea hydroperoxide or sodium percarbonate as the oxygen sources could make this reaction environmentally benign. In addition, one-pot direct organocatalytic asymmetric tandem epoxidation-Wittig reactions are described. The reactions were highly diastereo- and enantioselective and provide a rapid access to 2,4-diepoxy aldehydes. Moreover, a highly stereoselective one-pot organocatalytic asymmetric cascade epoxidation-Mannich reaction, which proceeds via the combination of iminium and enamine activation, is presented. The mechanism and stereochemistry of the amino acid- and chiral pyrrolidine-catalyzed direct asymmetric epoxidation of ,,,-unsaturated aldehydes are also discussed. [source] Olefin epoxidation by dioxiranes and percarboxylic acids: an analysis of activation energies calculated by a density functional methodJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 6 2001Philip Gisdakis Abstract The activity of dioxiranes, R2CO2, and percarboxylic acids, RCO(O2)H, in olefin epoxidation reactions can be rationalized by a frontier orbital interaction. Barrier heights of these oxygen transfer reactions, as calculated by a density functional method, depend linearly on the energy of the olefin HOMO orbital , (C,C) and of the peroxide LUMO orbital ,*(O,O). Activation barriers can be predicted from linear relationships with the proton affinity of a dioxirane (as measured by the hydrogen fluoride association energy) or the pKa value of a percarboxylic acid. Copyright © 2001 John Wiley & Sons, Ltd. [source] Functional syndiotactic poly(,-hydroxyalkanoate)s via stereoselective ring-opening copolymerization of rac -,-butyrolactone and rac -allyl-,-butyrolactoneJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 12 2009Noureddine Ajellal Abstract The copolymerization of racemic ,-butyrolactone (rac -BLMe) with racemic "allyl-,-butyrolactone" (rac -BLallyl) in toluene, catalyzed by the discrete amino-alkoxy-bis(phenolate) yttrium-amido complex 1, gave new poly(,-hydroxyalkanoate)s with unsaturated side chains. The poly(BLMe - co -BLallyl) copolymers produced have a highly syndiotactic backbone structure (Pr = 0.80,0.84) with a random enchainment of monomer units, as evidenced by 13C NMR, and high molecular weight (Mn up to 58,000 g mol,1) with a narrow polydispersity (Mw/Mn = 1.07,1.37), as determined by GPC. The comonomer incorporation (5,50 mol % rac -BLallyl) was a linear function of the feed ratio. The pendant vinyl bond of the side-chains in those poly(BLMe - co -BLallyl) copolymers allowed the effective introduction of hydroxy or epoxy groups via dihydroxylation, hydroboration-oxidation or epoxidation reactions. NMR studies indicated that all of these transformations proceed in an essentially quantitative conversion and do not affect the macromolecular architecture. Some thermal properties (Tm, ,Hm, Tg) of the prepared polymers have been also evaluated. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3177,3189, 2009 [source] Oxidation and epoxidation of poly(1,3-cyclohexadiene)JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 1 2003D. T. Williamson Abstract Poly(1,3-cyclohexadiene) (PCHD) derivatives were synthesized via facile chemical modification reactions of the residual double bond in the repeat unit. The oxidation and degradation of PCHD was investigated to enable subsequent controlled epoxidation reactions. PCHD exhibited a 15% weight loss at 110 °C in the presence of oxygen. The oxidative degradation, demonstrated by gel permeation chromatography (GPC) and 1H NMR spectroscopy, was attributed to main-chain scission. Aldehyde and ether functional groups were introduced into the polymer during the oxidation process. PCHD was quantitatively epoxidized in the absence of deleterious oxidation with meta -chloroperoxybenzoic acid. 1H and 13C NMR spectroscopy confirmed that polymers with controlled degrees of epoxidation were reproducibly obtained. Epoxidized PCHD exhibited a glass-transition temperature at 154 °C, which was slightly higher than that of a PCHD precursor of a nearly equivalent molecular weight. Moreover, GPC indicated the absence of undesirable crosslinking or degradation, and the molecular weight distributions remained narrow. The thermooxidative stability of the fully epoxidized polymer was compared to that of the PCHD precursor, and the epoxidized PCHD exhibited an initial weight loss at 250 °C in oxygen, which was 140 °C higher than the temperature for PCHD. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 84,93, 2003 [source] Dramatic Enhancement of Enone Epoxidation Rates in Nonionic MicroemulsionsCHEMISTRY - A EUROPEAN JOURNAL, Issue 29 2006Thomas Wielpütz Dipl.-Chem. Abstract The ability of microemulsions to dissolve polar and non-polar components with a huge internal interface can overcome the reagent incompatibilities frequently encountered in organic reactions. We investigated model epoxidation reactions of ,,,-unsaturated enones and alkaline hydrogen peroxide in different nonionic microemulsions, both in the presence and absence of a phase-transfer agent (PTA). The obtained reaction profiles were compared with those for the corresponding surfactant-free two-phase systems. In addition, we defined a time constant , as a measure for the rate of turnover. The epoxidation of trans -chalcone using an n -alkyl-polyoxyethylene surfactant based microemulsion was fastest in the system with the PTA (,=66 min) and slightly slower without the PTA (,=77 min). It was still slower in the two-phase system with a PTA (,=114 min) and extremely sluggish without a phase-transfer agent. With n -alkyl ,- D -glucopyranoside as the surfactant the conversion was twice as fast than in the former microemulsion systems, but the PTA did not accelerate the reaction further (,=35 and 33 min). The epoxidation of vitamin K3, the second model system, was extremely accelerated. It proceeded a factor of approximately 35 faster in the microemulsion (,=1.44 min) than in the corresponding two-phase system (,=57 min). [source] Ruthenium-Catalyzed Asymmetric Epoxidation of Olefins Using H2O2, Part II: Catalytic Activities and MechanismCHEMISTRY - A EUROPEAN JOURNAL, Issue 7 2006Man Kin Tse Dr. Abstract Asymmetric epoxidation of olefins with 30,% H2O2 in the presence of [Ru(pybox)(pydic)] 1 and [Ru(pyboxazine)(pydic)] 2 has been studied in detail (pybox=pyridine-2,6-bisoxazoline, pyboxazine=pyridine-2,6-bisoxazine, pydic=2,6-pyridinedicarboxylate). 35 Ruthenium complexes with sterically and electronically different substituents have been tested in environmentally benign epoxidation reactions. Mono-, 1,1-di-, cis - and trans -1,2-di-, tri-, and tetra-substituted aromatic olefins with versatile functional groups can be epoxidized with this type of catalyst in good to excellent yields (up to 100,%) with moderate to good enantioselectivies (up to 84,% ee). Additive and solvent effects as well as the relative rate of reaction with different catalysts have been established. It is shown that the presence of weak organic acids or an electron-withdrawing group on the catalyst increases the reactivity. New insights on the reaction intermediates and reaction pathway of the ruthenium-catalyzed epoxidation are proposed on the basis of density functional theory calculation and experiments. [source] | ||||||||||