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Quantitative Yields (quantitative + yield)
Selected AbstractsMetathesis in Pure Water Mediated by Supramolecular AdditivesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 3 2009Thomas Brendgen Abstract Supramolecular, water-soluble additives based on calix[n]arenes exhibit a beneficial influence on the ring-closing and cross metathesis of non-polar substrates in pure aqueous medium using standard Grubbs-II and Hoveyda-II catalysts. The catalytic activity observed in water is virtually the same as that in pure methanol. Quantitative yields of metathesis product can be achieved under mild aerobic conditions in/on water by (micro)solubilization of both the catalyst and starting materials by the macrocycles. [source] Nucleophilic Additions to Cyclic Nitrones en Route to Iminocyclitols , Total Syntheses of DMDP, 6-deoxy-DMDP, DAB-1, CYB-3, Nectrisine, and Radicamine BEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 17 2008Pedro Merino Abstract Highly diastereoselective nucleophilic additions to cyclic nitrones derived from L -malic acid and D -arabinose have been used for the construction of enantiomerically pure polyhydroxylated pyrrolidines. The synthetic strategy adopted was based on an oxidation/reduction protocol involving hydroxylamine/nitrone pairs and demonstrates the use of reagent- and substrate-derived stereocontrol. In most cases reactions took place with total diastereoselectivity and in quantitative yield, with no purification being necessary. By this strategy, 2-(hydroxymethyl)-, 2-(aminomethyl)-, and 2-aryl-substituted polyhydroxylated pyrrolidines have been prepared with abundant configurational diversity. The use of appropriate substrates and reagents allowed for approaches to DMDP, 6-deoxy-DMDP, DAB-1, CYB-3, nectrisine and radicamine B. Several analogues of these compounds with inverted configuration at one or more stereocenters were also prepared.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Synthesis and Structural Properties of New Oligodeoxynucleotide Analogues Containing a 2,,5,-Internucleotidic Squaryldiamide Linkage Capable of Formation of a Watson,Crick Base Pair with Adenine and a Wobble Base Pair with Guanine at the 3,-Downstream Junction SiteEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 10 2004Kousuke Sato Abstract A TpT dimer analogue (U2,sq5,T), in which the 3,-5, phosphodiester linkage was replaced by a 2,-5, squaryldiamide linkage and the 5,-upstream T was replaced by a 3,-deoxyuridine, was synthesized in almost quantitative yield from diethyl squarate. This new dimer structural motif was designed to eliminate the squaryldiamide skeleton-induced overall strain in T3,sq5,T, previously incorporated into DNA fragments as a new TpT mimic, through the change in the connection mode from the 3,-5, linkage to a 2,-5, linkage. Spectral analyses of U2,sq5,T suggest that the overall structure of this dimer mimic is basically similar to that of TpT. A DNA 10mer 5,-d(CGCAU2,sq5,TAGCC)-3, incorporating this dimer was synthesized. From the CD analysis, it turned out that the overall structure of a DNA duplex of 5,-d(CGCAU2,sq5,TAGCC)-3,/3,-d(GCGTAATCGG)-5, is closer to that of the unmodified duplex than the DNA duplex of 5,-d(CGCAT3,sq5,TAGCC)-3,/3,-d(GCGTAATCGG)-5,. Interestingly, extensive Tm experiments suggest that d(CGCAU2,sq5,TAGCC)-3, exhibits intriguing inherent hybridization affinity not only for the completely complementary oligodeoxynucleotide 3,-d(GCGAATCGG)-5,, but also for 3,-d(GCGTAGTCGG)-5,, with a mismatched dG. The unique property of the 3,-downstream dT moiety of U2,sq5,T , the ability to recognize both dA and dG , was also supported by more detailed computational analysis of U2,sq5,T and TpT. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Primary Amine-Thioureas based on tert -Butyl Esters of Natural Amino Acids as Organocatalysts for the Michael ReactionADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2009Christoforos Abstract A new class of primary amine-thioureas based on tert -butyl esters of (S)-,-amino acids and (1S,2S)-diphenylethylenediamine was synthesized and their activity as catalysts in Michael additions was evaluated. Derivatives based on di- tert -butyl aspartate and tert -butyl O - tert -butyl threoninate provided the product of the reaction between trans- ,-nitrostyrene and acetone in quantitative yield and high enantioselectivity (87,91% ee). All the thioureas based on tert -butyl esters of amino acids catalyzed the reaction of nitroolefins with acetophenone with high enantioselectivity (92,98% ee). Thus, low-cost, commercially available tert -butyl esters of natural amino acids are very important chiral building blocks for the construction of novel chiral thioureas able to catalyze asymmetric Michael additions with high enantioselectivity. [source] A Lutidine-Bridged Bis-Perimidinium Salt: Synthesis and Application as a Precursor in Palladium-Catalyzed Cross-Coupling ReactionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 7-8 2009Tao Tu Abstract A novel lutidine-bridged bis-perimidinium dibromide 3 was synthesized in quantitative yield from cheap commercial starting materials. The bisylidene prepared therefrom in situ upon deprotonation is a potent precatalyst in palladium-catalyzed Heck and Suzuki cross-coupling reactions under aerobic conditions, and is efficient even with a ppm scale catalyst loading. Its stronger ,-donor character is held to be responsible for its superior catalytic performance compared with imidazole- and benzimidazole-based analogues bearing the same skeleton precursors. [source] Hybrid Inorganic-Organic Materials Carrying Tertiary Amine and Thiourea Residues Tethered on Mesoporous Silica Nanoparticles: Synthesis, Characterization, and Co-Operative CatalysisADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2009Alessandra Puglisi Abstract Mesoporous silica nanoparticles carrying different loadings of tertiary amine and thiourea residues (residues ratios 53/47, 68/32, and 22/78, respectively) were synthesized by the co-condensation method and fully characterized by CP MAS NMR, powder XRD, SEM, BET, BJH and FT-IR techniques. These materials were tested as bifunctional catalysts in the conjugate addition of acetylacetone to 2-nitrostyrene, a reaction that under solvent-free conditions occurred in quantitative yield. By carrying out several experiments with the bifunctional catalysts featuring different molar ratios of active sites, and with different combinations of monofunctional supported and non-supported catalyst, the co-operativity of the tertiary amine and thiourea residues in catalyzing the reaction was demonstrated. The use of the bifunctional catalyst was extended to the addition of acetylacetone to an activated imine. Catalyst recycling for a total of three reaction cycles was demonstrated without significant erosion of activity. [source] Silver-Catalyzed Rearrangement of Propargylic Sulfinates to Allenic SulfonesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 7-8 2008Michael Harmata Abstract Treatment of propargylic sulfinate esters with 2 mol,% of silver hexafluoroantimonate results in the rapid formation of allenic sulfones in essentially quantitative yield. [source] Triphase Hydrogenation Reactions Utilizing Palladium-Immobilized Capillary Column Reactors and a Demonstration of Suitability for Large Scale SynthesisADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 15 2005Juta Kobayashi Abstract We have developed a practical and highly productive system for hydrogenation reactions utilizing capillary column reactors, which occupy less space than ordinary batch systems, are low cost and easy to handle, and show feasibility toward large-scale chemical synthesis. Palladium-containing micelles were immobilized onto the inner surface of the capillaries. Nine palladium-immobilized capillaries were assembled and connected to a T-shaped connector, and hydrogen and a substrate solution were fed to capillaries via the connector. Hydrogenation of 1-phenyl-1-cyclohexene (1) proceeded smoothly to give phenylcyclohexane in quantitative yield. The capillaries themselves occupy only ca. 0.4,mL and a high space-time yield has been achieved (124.3,mg/17,min/0.4,mL). In addition, leaching of palladium was not detected by ICP analysis after reactions. [source] Chemo-Enzymatic Approach to Statin Side-Chain Building BlocksADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 6-7 2003R. Öhrlein Abstract A versatile statin side-chain building block is obtained by an enzymatic desymmetrisation of the symmetrical glutaric acid diethyl ester. The monoacid is produced in almost quantitative yield in the desired high optical purity. The monoacid is easily converted to the corresponding acid chloride, which is a key compound to be elaborated to some statin side-chain derivatives. The optically active C-5 chain is subsequently elongated by two carbon atoms and syn -reduced to the final diol fragment. [source] Comparison of micelles formed by amphiphilic star block copolymers prepared in the presence of a nonmetallic monomer activatorJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 6 2008Hoon Hyun Abstract In this article, we describe the synthesis of PEG- b -polyester star block copolymers via ring-opening polymerization (ROP) of ester monomers initiated at the hydroxyl end group of the core poly(ethylene glycol) (PEG) using HCl Et2O as a monomer activator. The ROP of ,-caprolactone (CL), trimethylene carbonate (TMC), or 1,4-dioxan-2-one (DO) was performed to synthesize PEG- b -polyester star block copolymers with one, two, four, and eight arms. The PEG- b -polyester star block copolymers were obtained in quantitative yield, had molecular weights close to the theoretical values calculated from the molar ratio of ester monomers to PEG, and exhibited monomodal GPC curves. The crystallinity of the PEG- b -polyester star block copolymers was determined by differential scanning calorimetry and X-ray diffraction. Copolymers with a higher arm number had a higher tendency toward crystallization. The crystallinity of the PEG- b -polyester star block copolymers also depended on the nature of the polyester block. The CMCs of the PEG- b -PCL star block copolymers, determined from fluorescence measurements, increased with increasing arm number. The CMCs of the four-arm star block copolymers with different polyester segments increased in the order 4a-PEG- b -PCL < 4a-PEG- b -PDO < 4a-PEG- b -PLGA < 4a-PEG- b -PTMC, suggesting a relationship between CMC and star block copolymer crystallinity. The partition equilibrium constant, Kv, which is an indicator of the hydrophobicity of the micelles of the PEG-polyester star block copolymers in aqueous media, increased with decreasing arm number and increasing crystallinity. A key aspect of the present work is that we successfully prepared PEG- b -polyester star block copolymers by a metal-free method. Thus, unlike copolymers synthesized by ROP using a metal as the monomer activator, our copolymers do not contain traces of metals and hence are more suitable for biomedical applications. Moreover, we confirmed that the PEG- b -polyester star block copolymers form micelles and hence may be potential hydrophobic drug delivery vehicles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2084,2096, 2008 [source] Biodegradable Hyaluronic Acid/N -Carboxyethyl Chitosan/Protein Ternary Complexes as Implantable Carriers for Controlled Protein ReleaseMACROMOLECULAR BIOSCIENCE, Issue 12 2005Hongliang Jiang Abstract Summary: An ampholytic N -carboxyethyl chitosan (CEC), with various isoelectric points (IPs), was synthesized by grafting acrylic acid on chitosan utilizing Michael's reaction. Compared to native chitosan, CEC has enhanced water solubility and dramatically accelerated enzymatic degradation; the rate of degradation is proportional to the degree of substitution (DS). The results from turbidimetric titration and fluorescence studies revealed that CEC formed complexes with either hyaluronic acid (HA) or bovine serum albumin (BSA) within a certain pH range. The HA/CEC/BSA ternary complexes could be prepared by colloid titration with quantitative yield and BSA entrapment. The rate of BSA release from the complexes was affected by pH, ionic strength, DS of CEC, and the molecular weight (MW) of HA. The endurance of BSA release from the complexes could be extended up to 20 d by formulating them with high-MW HA and CEC with low DS. BSA release profiles from HA/CEC-2/BSA complexes. [source] Topochemically controlled solid-state methyl rearrangement in thiocyanuratesACTA CRYSTALLOGRAPHICA SECTION B, Issue 3 2001Mark Greenberg 4,6-Dimethoxy-3-methyl-1,3,5-triazine-2(3H)-thione crystallizes in two polymorphic forms, needles and plates. In the needle-shaped crystals (9a) the molecules occupy the crystallographic mirror plane, thus the layers are stacked along the b axis. The molecules of the other polymorph [plate-shape crystals, (9b)] are packed in a herringbone packing mode. Upon heating, (9b) undergoes a phase transition to form (9a). At 378,K the needles undergo O , S topochemically controlled methyl transfer in the solid state to produce 1-methyl-4-methoxy-6-methylthio-1,3,5-triazine-2(1H)-one in 75% yield. The enthalpy of the rearrangement is estimated to be ,39.1,kJ,mol,1. 1-Methyl-6-methoxy-4-methylthio-1,3,5-triazine-2(1H)-thione crystallizes in space group P21 with two crystallographically independent molecules in the asymmetric unit. Compound (9b) undergoes O , S methyl transfer in the solid state at 373,K. The rearrangement is topochemically assisted and the product, 1-methyl-2,4-bismethylthio-1,3,5-triazine-6(1H)-one, is obtained in quantitative yield. The enthalpy of the rearrangement is estimated to be ,58.8,kJ,mol,1. The crystal structures of the compounds as well as their DSC thermographs are described and discussed. Energy calculation by ab initio methods shows that the driving force for the reactions is the difference between the molecular energies of the pre-rearranged compounds and their products, 54.2 and 59.3,kJ,mol,1 in the two cases, respectively. [source] Metal Ions Drive Thermodynamics and Photochemistry of the Bis(styryl) Macrocyclic TweezerCHEMISTRY - A EUROPEAN JOURNAL, Issue 19 2010Elena Abstract UV/Vis and NMR spectroscopy were used for the structural elucidation and thermodynamic and photochemical studies of the metal-coordinated crown-containing macrocyclic tweezer (E,E)- 1. The bis(styryl) tweezer (E,E)- 1 formed two types of complexes with magnesium(II): a 1:1 intramolecular asymmetric sandwich complex [(E,E)- 1],Mg2+ and a 1:2 complex [(E,E)- 1],(Mg2+)2. In the former case, there is direct cation intramolecular exchange (0.299,s,1, ,G,=69.4,kJ,mol,1) between two parts of the bis(styryl) tweezer (E,E)- 1. Addition of barium(II) to the bis(styryl) tweezer (E,E)- 1 led to an intramolecular centrosymmetric sandwich 1:1 complex [(E,E)- 1],Ba2+. Irradiation of [(E,E)- 1],Ba2+ afforded reversible intramolecular [2,+2,] photocyclization with excellent stereoselectivity and quantitative yield. In contrast, irradiation of [(E,E)- 1],(Mg2+)2 resulted in reversible stepwise E,Z -isomerization. [source] A Dynamic Tricopper Double HelicateCHEMISTRY - A EUROPEAN JOURNAL, Issue 15 2006Marie Hutin Abstract The reaction between 8-aminoquinoline, 1,10-phenantholine-2,9-dicarbaldehyde, and copper(I) tetrafluoroborate gave a quantitative yield of a tricopper double helicate. The presence of dynamic covalent imine (CN) bonds allowed this assembly to participate in two reactions not previously known in helicate chemistry: 1) It could be prepared through subcomponent substitution from a dicopper double helicate that contained aniline residues. An electron-poor aniline was quantitatively displaced; a more electron-rich aniline competed effectively with the aminoquinoline, setting up an equilibrium between dicopper and tricopper helicates that could be displaced towards the tricopper through the addition of further copper(I). 2) Both dicopper and tricopper helicates could be prepared simultaneously from a mixture of phenanthroline dialdehyde, aniline, and aminoquinoline, which contained all possible imine condensation products in equilibrium. Following the addition of copper(I), thermodynamic equilibration on both covalent and coordinative levels eliminated all partially-formed and mixed imine ligands from the mixture, leaving the helicates as exclusive products. La réaction entre la 8-aminoquinoline, la 1,10-phenanthroline-2,9-dicarbaldehyde et le cuivre(i,) tetrafluoroborate conduit à la formation quantitative d'un double hélicate à trois cuivres. Grâce à la liaison imine (CN) dynamique et covalente, cet assemblage participe à deux réactions nouvelles dans la chimie des hélicates : 1) L'hélicate peut être préparé par la substitution de composants à partir d'un double hélicate à deux cuivres incorporant des anilines. Une aniline pauvre en électrons est déplacée quantitativement par l'aminoquinoline ; une aniline plus riche en électrons est déplacée plus difficilement, conduisant ainsi à un équilibre entre l'hélicate à deux cuivres et celui à trois cuivres. Cet équilibre peut être déplacé vers la formation de l'hélicate à trois cuivres par l'addition d'un excès de cuivre(i,). 2) Les hélicates à deux et trois cuivres peuvent être préparés simultanément en ajoutant du cuivre(i,) à un mélange d'aminoquinoline, d'aniline et de phenanthrolinecarbaldehyde contenant tous les produits de condensation possibles à l'équilibre. Suite à cet ajout, l'équilibre thermodynamique élimine les ligands partiellement formés ou mixtes, laissant les hélicates comme uniques produits. [source] Synthesis of Aminophosphine Ligands with Binaphthyl Backbones for Silver(I)-catalyzed Enantioselective Allylation of Benzaldehyde,CHINESE JOURNAL OF CHEMISTRY, Issue 11 2002Yi Wang Abstract A series of aminophosphine ligands was synthesized from 2-amino-2,-hydroxy-1,1,-binaphthyl (NOBIN). Their asymmetric induction efficiency was examined for silver(I) catalyzed enantioselective allylation reaction of benzaldehyde with allyltributyltin. Under the optimized reaction conditions, quantitative yield as well as moderate ee value (54.5% ee) of product was achieved by the catalysis with silver(I)/3 complex. The effects of the binaphthyl backbone and the substitutes situated at chelating N, P atoms on enantioselectivity of the reaction were also discussed. [source] Dinuclear Potassium-Chromium and Potassium-Tungsten Carbonyl ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2004Vladimir Kirin Abstract The tetracarbonyl complexes [M(CO)4{,2 -(Ph2P)2NH}] [M = Cr (1a), W (1b)] have been synthesised by reaction of M(CO)6, Me3NO·2H2O, and (Ph2P)2NH. Subsequent treatment of complexes 1a,b with an excess of KH in THF at room temperature yields the potassium salts [Cr(CO)4{,2 -(Ph2P)2N}K(THF)3]n (2a) and [W(CO)4{,2 -(Ph2P)2N}K(THF)2]n (2b), respectively, in almost quantitative yields. The ionic compounds 2a,b are stable at room temperature. All four compounds 1a,b and 2a,b were characterised by single-crystal X-ray diffraction. Compounds 2a,b form infinite chains via isocarbonyl bridges in the solid state. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Pyridine-facilitated phenylselenoetherification of some tertiary alkenolsHETEROATOM CHEMISTRY, Issue 6 2001Biljana M. Mojsilovic An improved procedure for intramolecular cyclization of tertiary alkenols using benzeneselenyl halides has been developed. We found that cyclization can be facilitated by pyridine. Thus, in the presence of an equimolar amount of pyridine, a chemospecific reaction could be observed that resulted in formation of corresponding cyclic ethers, and quantitative yields were achieved instantaneously under extremely mild experimental conditions. The effect of the halide ion of the selenylating reagent is not significant, both halides generally giving equal results © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:475,479, 2001 [source] Lewis Basic Ionic Liquids-Catalyzed Conversion of Carbon Dioxide to Cyclic CarbonatesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2010Zhen-Zhen Yang Abstract A series of easily prepared Lewis basic ionic liquids were developed for cyclic carbonate synthesis from epoxide and carbon dioxide at low pressure without utilization of any organic solvents or additives. Notably, quantitative yields together with excellent selectivity were attained when 1,8-diazabicyclo[5.4.0]undec-7-enium chloride ([HDBU]Cl) was used as a catalyst. Furthermore, the catalyst could be recycled over five times without appreciable loss of catalytic activity. The effects of the catalyst structure and various reaction parameters on the catalytic performance were investigated in detail. This protocol was found to be applicable to a variety of epoxides producing the corresponding cyclic carbonates in high yields and selectivity. Therefore, this solvent-free process thus represents an environmentally friendly example for the catalytic conversion of carbon dioxide into value-added chemicals by employing Lewis basic ionic liquids as catalyst. A possible catalytic cycle for the hydrogen bond-assisted ring-opening of epoxide and activation of carbon dioxide induced by the nucleophilic tertiary nitrogen of the ionic liquid was also proposed. [source] Highly Enantioselective Hydrogenation of Quinoline and Pyridine Derivatives with Iridium-(P-Phos) CatalystADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 6 2010Wei-Jun Tang Abstract The use of a chiral iridium catalyst generated in situ from the (cyclooctadiene)iridium chloride dimer, [Ir(COD)Cl]2, the P-Phos ligand [4,4,-bis(diphenylphosphino)-2,2,,6,6,-tetramethoxy-3,3,-bipyridine] and iodine (I2) for the asymmetric hydrogenation of 2,6-substituted quinolines and trisubstituted pyridines [2-substituted 7,8-dihydroquinolin-5(6H)-one derivatives] is reported. The catalyst worked efficiently to hydrogenate a series of quinoline derivatives to provide chiral 1,2,3,4-tetrahydroquinolines in high yields and up to 96% ee. The hydrogenation was carried out at high S/C (substrate to catalyst) ratios of 2000,50000, reaching up to 4000,h,1 TOF (turnover frequency) and up to 43000 TON (turnover number). The catalytic activity is found to be additive-controlled. At low catalyst loadings, decreasing the amount of additive I2 was necessary to maintain the good conversion. The same catalyst system could also enantioselectively hydrogenate trisubstituted pyridines, affording the chiral hexahydroquinolinone derivatives in nearly quantitative yields and up to 99% ee. Interestingly, increasing the amount of I2 favored high reactivity and enantioselectivity in this case. The high efficacy and enantioselectivity enable the present catalyst system of high practical potential. [source] 3,5-Bis(n -perfluorooctyl)benzyltriethylammonium Bromide (F-TEBA): An Efficient, Easily Recoverable Fluorous Catalyst for Solid-Liquid PTC ReactionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 18 2009Gianluca Pozzi Abstract A readily available 3,5-bis(perfluorooctyl)benzyl bromide and triethylamine were reacted under mild conditions to give 3,5-bis(n -perfluorooctyl)benzyltriethylammonium bromide (F-TEBA), an analogue of the versatile phase-transfer catalyst, benzyltriethylammonium chloride (TEBA), containing two fluorous ponytails. This perfluoroalkylated quaternary ammonium salt was successfully employed as a catalyst in a variety of reactions run under solid-liquid phase-transfer catalysis (SL-PTC) conditions. Thus, being both hydrophobic and lipophobic, F-TEBA could be quickly recovered in quantitative yields, and reused without loss of activity over several reaction cycles. [source] Highly Efficient Synthesis of New ,-Arylamino-,,-chloropropan-2-ones via Oxidative Hydrolysis of Vinyl Chlorides Promoted by Calcium HypochloriteADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 18 2009Vittorio Pace Abstract The oxidative hydrolysis of different trifluoroacetyl-protected N -(2-chloroallyl)anilines, promoted by calcium hypochlorite, is able to yield several not previously described ,-arylamino-,,-chloropropan-2-ones, very valuable building blocks that are useful as precursors of several drugs, in excellent yields and short reaction times. The main requirement of the reaction for avoiding the undesired aromatic chlorination (N -protection) is effectively solved by the use of the easily formed and removed N -trifluoroacetyl group. Thus, it is possible to perform the oxidative hydrolysis-deprotection step using a one-pot strategy, obtaining quantitative yields in very short reaction times. [source] Highly Selective Oxidation of Alkylphenols to Benzoquinones with Hydrogen Peroxide over Silica-Supported Titanium Catalysts: Titanium Cluster Site versus Titanium Single SiteADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2009Oxana Abstract Titanium-silica catalysts have been prepared by supporting titanium(IV) precursors with different nuclearity {mononuclear titanocene dichloride Ti(Cp)2Cl2, dinuclear titanium diethyl tartrate and the tetranuclear titanium peroxo complex (NH4)8[Ti4(C6H4O7)4(O2)4],8,H2O} onto the surface of silica materials with different textural characteristics. The supported catalysts have been explored as highly active and reusable catalysts for the oxidation of 2,3,6-trimethylphenol (TMP) and 2,6-dimethylphenol (DMP) to 2,3,5-trimethyl-1,4-benzoquinone (TMBQ, vitamin E key intermediate) and 2,6-dimethyl-1,4-benzoquinone (DMBQ), respectively, using aqueous hydrogen peroxide as green oxidant. Catalysts prepared by grafting mononuclear Ti(Cp)2Cl2 revealed a strong dependence of the product selectivity on the surface concentration of titanium active centers. Mesoporous materials with titanium surface concentration in the range of 0.6,1.0,Ti/nm2 were identified as optimal catalysts for the transformation of alkylphenols to benzoquinones. Catalysts having <0.6,Ti/nm2 produced a mixture of benzoquinones and dimeric by-products. Conversely, when di-/tetranuclear titanium precursors were employed for the catalyst preparation, a diminution of the titanium surface concentration had no impact on the benzoquinone selectivity, which was typically as high as 96,99%. DR-UV spectroscopic studies revealed that the catalysts capable of producing alkylbenzoquinones with nearly quantitative yields possess titanium dimers and/or subnanometer-size clusters homogeneously distributed on a silica surface. On the contrary, catalysts with isolated titanium sites give a considerable amount of dimeric by-products. This is the first example which clearly demonstrates the advantages of titanium cluster-site catalysts over titanium single-site catalysts in hydrogen peroxide-based selective oxidation reaction. [source] Efficient Biocatalytic Cleavage and Recovery of Organic Substrates Supported on Soluble PolymersADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 6 2007Dario Pasini Abstract The applicability of novel solution-phase supports in combination with enzymes for biocatalytic transformations is reported. Ex novo designed styrene-based copolymers, bearing a phenylacetic residue in variable loadings and linked as a pendant group to the macromolecular backbone, through a spacer of variable length, have been synthesized and characterized. These derivatives are compatible and can be used as soluble supports in combination with immobilized penicillin G acylase (PGA , EC 3.5.1.11) for the biocatalytic cleavage of the covalently anchored organic substrate in quantitative yields, in water or water/dimethylformamide solvent mixtures, with recovery of the immobilized enzyme with negligible losses in activity. [source] Stille Reactions with Tetraalkylstannanes and Phenyltrialkylstannanes in Low Melting Sugar-Urea-Salt MixturesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 15 2006Giovanni Imperato Abstract The transfer of simple alkyl groups in Stille reactions usually requires special solvents (HMPA) or certain organotin reagents (stannatranes, monoorganotin halides) to be efficient. Using low-melting mixtures of sugar, urea and inorganic salt as solvent, a fast and efficient palladium-catalyzed alkyl transfer with tetraalkyltin reagents was observed. The high polarity and nucleophilic character of the solvent melt promotes the reaction. Stille biaryl synthesis using electron-poor and electron-rich aryl bromides proceeds with quantitative yields in the sugar-urea-salt melt. Catalyst loading may be reduced to 0.001 mol,% and the catalyst melt mixture remains active in several reaction cycles. Showing the same or improved performance for Stille reactions than organic solvents and allowing a very simple work up, sugar-urea-salt melts are a non-toxic and cheap alternative reaction medium available in bulk quantities for the catalytic process. [source] Synthesis and characterization of poly[phenyl(fluoroalkyloxaalkane)silanediyl]sJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2003Vjacheslav V. Zuev Abstract Monomeric fluoroalkoxyalkyl(phenyl)dichlorosilanes were synthesized with quantitative yields by hydrosilylation of allyl ethers of fluoroalcohols with phenyldichlorosilane with Pt(Ph3Sb)2Cl2 complex as a catalyst. Starting from these monomers, corresponding polysilanes with weight-average molecular weights of 2,3 × 104 were obtained by the Wurtz reaction. Increasing the CF2 groups containing two to six monomer units caused the char yields to increase from 3 to 48% at 800 °C in air. The emission characteristics of these polysilanes in a chloroform solution were examined. They had a narrow peak at 344 nm with a small Stokes shift (,20 nm). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3761,3767, 2003 [source] Anionic polymerization of methyl methacrylate initiated with late transition-metal halides/organolithium/triisobutylaluminum systemsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2003Eiji Ihara Abstract Anionic polymerization of methyl methacrylate (MMA) initiated with late transition-metal halides [manganese chloride (MnCl2), iron dichloride (FeCl2), iron trichloride (FeCl3), cobalt chloride (CoCl2), or nickel bromide (NiBr2)]/organolithium [nButyllithium (nBuLi) or phenyllithium (PhLi)]/triisobutylaluminum (iBu3Al) systems is described. Except for the system with NiBr2, the polymerizations of MMA afforded narrow molecular weight distribution poly(methyl methacrylate)s (PMMAs) with high molecular weights in quantitative yields at 0 °C in toluene. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) analyses of the PMMAs obtained by the systems with FeCl2, FeCl3, and CoCl2 revealed that the polymers had hydrogen (H) at both chain ends. Accordingly, the reaction of the transition-metal halides with the organolithium in the presence of iBu3Al should result in the formation of transition-metal hydride [M-H], species, which was nucleophilic enough to initiate the MMA polymerization. Because the presence of a six-membered cyclic structure resulting from backbiting was confirmed from the MALDI-TOF MS analyses of the PMMA obtained with the metal halide (FeCl2, FeCl3, or CoCl2)/organolithium systems in the absence of iBu3Al, the introduction of H at the ,-chain end indicated that iBu3Al should prevent the backbiting. However, the MnCl2/nBuLi/iBu3Al initiating system gave PMMAs bearing H at the , chain end and six-membered cyclic structure at the , chain end. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1962,1977, 2003 [source] Synthesis of well-defined poly(N -isopropylacrylamide) by the anionic polymerization of N -methoxymethyl- N -isopropylacrylamideJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2002Takashi Ishizone The anionic polymerization of N -methoxymethyl- N -isopropylacrylamide (1) was carried out with diphenylmethylpotassium in the presence of Et2Zn in tetrahydrofuran at ,78 °C for 20 h. Poly(1)s, having predicted molecular weights and narrow molecular weight distributions (weight-average molecular weight/number-average molecular weight < 1.1), were obtained in quantitative yields. The methoxymethyl protecting group of the resultant poly(1)s was completely removed, and this yielded poly(N -isopropylacrylamide) possessing well-defined chain structures because of treatment with aqueous hydrochloric acid in 1,4-dioxane at room temperature for 20 h. [source] Microwave-assisted synthesis and characterization of heterocyclic, and optically active poly(amide-imide)s incorporating L -amino acidsPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 12 2008Abdol R. Hajipour Abstract N,N,-Pyromelliticdiimido-di- L -alanine (1), N,N,-pyromelliticdiimido-di- L -phenylalanine (2), and N,N,-pyromelliticdiimido-di- L -leucine (3) were prepared from the reaction of pyromellitic dianhydride with corresponding L -amino acids in a mixture of glacial acetic acid and pyridine solution (3/2 ratio) under refluxing conditions. The microwave-assisted polycondensation of the corresponding diimide-diacyl chloride monomers (5,7) with 4-phenyl-2,6-bis(4-aminophenyl) pyridine (10) or 4-(p -methylthiophenyl)-2,6-bis(4-aminophenyl) pyridine (12) were carried out in a laboratory microwave oven. The resulting poly(amide-imide)s were obtained in quantitative yields, and they showed admirable inherent viscosities (0.12,0.55 dlg,1), were soluble in polar aprotic solvents, showed good thermal stability and high optical purity. The synthetic compounds were characterized by IR, MS, 1H NMR, and 13C NMR spectroscopy, elemental analysis, and specific rotation. Copyright © 2008 John Wiley & Sons, Ltd. [source] Organocatalytic synthesis of cyanohydrin trimethylsilyl ethers by potassium 4-benzylpiperidinedithiocarbamate under solvent-free conditionsAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 3 2010Mohammad G. Dekamin Abstract Potassium 4-benzylpiperidinedithiocarbamate was found to be an efficient organocatalyst for facile addition of trimethylsilyl cyanide to a wide variety of aldehydes and ketones to afford corresponding cyanohydrin trimethylsilyl ethers in high to quantitative yields. The reaction proceeded smoothly by employing 2.0 mol% PBPDC loading under mild conditions at room temperature within a very short reaction time. Copyright © 2009 John Wiley & Sons, Ltd. [source] A Resonance Energy Transfer Immunoassay Based on a Thiol-Reactive Ruthenium Donor Dye and a Longwave-Emitting AcceptorCHEMBIOCHEM, Issue 1 2007Jochen Weh Abstract A novel immunoassay is described that applies a thiol-reactive ruthenium metal,ligand complex as the donor dye in a luminescence energy transfer (LET) detection scheme. Unlike amine-reactive labels, the LET with a thiol label allows improved specificity and better reproducibility of labelling positions on proteins, because the number of reactive thiol groups of proteins is distinctly smaller. This helps to reduce the risk of over-labelling and self-quenching of the fluorophore. The synthesis of the thiol label was significantly improved, resulting in almost quantitative yields of pure product. The absorption and emission maxima of the ruthenium donor dye are at 460 nm and 600 nm, respectively, and a Stokes' shift of 140 nm warrants distinct separation of excitation and emission wavelengths even in turbid samples. A cyanine dye with an absorption maximum at 642 nm was chosen as the acceptor label because it has good overlap with the emission spectrum of the donor label. The emission of the acceptor peaks at 660 nm, thus further increasing the Stokes' shift (to an overall 200 nm). The quantification of anti-HSA with the LET immunoassay is possible with this new approach at concentrations as low as 220 pmol,L,1. [source] | ||||||||||||||||||||||||||||