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Very Efficient Catalyst (very + efficient_catalyst)
Selected AbstractsDonor-Stabilized Phosphenium Adducts as New Efficient and Immobilizing Ligands in Palladium-Catalyzed Alkynylation and Platinum-Catalyzed Hydrogenation in Ionic LiquidsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2009Samer Saleh Abstract The straightforward synthesis of a new donor-stabilized phosphenium ligand 3d by addition of bromodifurylphosphine to 1,3-dimethylimidazolium-2-carboxylate 1 is described. The obtained ligand exhibits a very strong ,-acceptor character, comparable to that of triphenyl phosphite [P(OPh)3] or of tris-halogenophosphines, with a ,CO(A1) at 2087,cm,1 for its nickel tricarbonyl complex. This ligand, as well as the related 3a which was obtained from chlorodiphenylphosphine, were tested in palladium-catalyzed aryl alkynylation and in the platinum-catalyzed selective hydrogenation of chloronitrobenzenes, both in an ionic liquid phase. In CC bond cross-coupling we observed that the increase of the ,-acceptor character in ligand 3d, due to the introduction of an additional electron-withdrawing group, provides a very efficient catalyst in the alkynylation reaction of aryl bromides with phenylacetylene, including the deactivated 4-bromoanisole or the sterically hindered 2-bromonaphthalene. The catalytic activity decreases with recycling due to the sensitiveness of ligands to protonation in the ionic phase. Conversely, a multiple recycling of the metal/ligand system in non-acidic media was achieved from platinum-catalyzed hydrogenation of m- chloronitrobenzene. The catalytic results obtained by employing the complex of platinum(II) chloride with 3a [trans -PtCl2(3a)2] in comparison with the non-ionic related trans -tris(triphenylphosphine)platinum dichloride [trans -PtCl2(PPh3)2] complex clearly indicate that the simultaneous existence of a strong ,-acceptor character and a positive charge within the ligand 3a significantly increases the life-time of the platinum catalyst. The selectivity of the reaction is also improved by decreasing the undesirable formation of dehalogenation products. This cationic platinum complex trans -PtCl2(3a)2 is the first example of a highly selective catalyst for hydrogenation of chloronitroarenes immobilized in an ionic liquid phase. The system was recycled six times without noticeable metal leaching in the organic phase, and no loss of activity. [source] Titanium-mediated [CpTiCl2(OEt)] ring-opening polymerization of lactides: A novel route to well-defined polylactide-based complex macromolecular architecturesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 5 2010Nikolaos Petzetakis Abstract Among three cyclopentadienyl titanium complexes studied, CpTiCl2(OEt), containing a 5% excess CpTiCl3, has proven to be a very efficient catalyst for the ring-opening polymerization (ROP) of L -lactide (LLA) in toluene at 130 °C. Kinetic studies revealed that the polymerization yield (up to 100%) and the molecular weight increase linearly with time, leading to well-defined PLLA with narrow molecular weight distributions (Mw/Mn , 1.1). Based on the above results, PS- b -PLLA, PI- b -PLLA, PEO- b -PLLA block copolymers, and a PS- b -PI- b -PLLA triblock terpolymer were synthesized. The synthetic strategy involved: (a) the preparation of OH-end-functionalized homopolymers or diblock copolymers by anionic polymerization, (b) the reaction of the OH-functionalized polymers with CpTiCl3 to give the corresponding Ti-macrocatalyst, and (c) the ROP of LLA to afford the final block copolymers. PMMA- g -PLLA [PMMA: poly(methyl methacrylate)] was also synthesized by: (a) the reaction of CpTiCl3 with 2-hydroxy ethyl methacrylate, HEMA, to give the Ti-HEMA-catalyst, (b) the ROP of LLA to afford a PLLA methacrylic-macromonomer, and (c) the copolymerization (conventional and ATRP) of the macromonomer with MMA to afford the final graft copolymer. Intermediate and final products were characterized by NMR spectroscopy and size exclusion chromatography, equipped with refractive index and two-angle laser light scattering detectors. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1092,1103, 2010 [source] Therapeutic applications of glycosidic carbonic anhydrase inhibitorsMEDICINAL RESEARCH REVIEWS, Issue 3 2009Jean-Yves Winum Abstract The zinc enzymes carbonic anhydrases (CAs, EC 4.2.1.1) are very efficient catalysts for the reversible hydration of carbon dioxide to bicarbonate and hence play an important physiological role. In humans, 16 different isozymes have been described, some of them being involved in various pathological disorders. Several of these isozymes are considered as drug targets, and the design of selective inhibitors is a long-standing goal that has captured the attention of researchers for 40 years and has lead to clinical applications against different pathologies such as glaucoma, epilepsy, and cancer. Among the different strategies developed for designing selective CA inhibitors (CAIs), the "sugar approach" has recently emerged as a new attractive and versatile tool. Incorporation of glycosyl moieties in different aromatic/heterocyclic sulfonamide/sulfamides/sulfamates scaffolds has led to the development of numerous and very effective inhibitors of potential clinical value. The clinical use of a highly active carbohydrate-based CA inhibitor, i.e., topiramate, constitutes an interesting demonstration of the validity of this approach. Other carbohydrate-based compounds also demonstrate promising potential for the treatment of ophthalmologic diseases. This review will focus on the development of this emerging sugar-based approach for the development of CAIs. © 2008 Wiley Periodicals, Inc. Med Res Rev, 29, No. 3, 419-435, 2009 [source] Synthesis of Dendritic BINAP Ligands and Their Applications in Asymmetric HydrogenationCHINESE JOURNAL OF CHEMISTRY, Issue 11 2002Guo-Jun Deng Abstract A new type of chiral dendritic ligands with 2,2,-bis(diphenylphosphino)-1,1,-binaphthyl (BINAP) located at the focal point of the dendrimer has been synthesized through the condensation reaction of 5-amino BINAP and Fréchet-type poly (aryl ether) dendrons with carboxyl groups as the linker in high reaction yields, respectively. The ruthenium complexes of these dendritic ligands were found to be very efficient catalysts in asymmetric hydrogenation of 2-phenylacryclic acids as well as facile catalyst recycling. [source] |