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Bis- as well as tris-tetrahydropyranone ring systems were obtained via multiple tandem cyclization-1,3-dipolar cycloaddition reactions of α-diazo ketones with ketone as well as aldehyde functional groups in a chemoselective manner. 相似文献
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Stopped-flow Fourier transform infrared spectroscopy of nitromethane oxidation by the diiron(IV) intermediate of methane monooxygenase 总被引:1,自引:0,他引:1
Muthusamy M Ambundo EA George SJ Lippard SJ Thorneley RN 《Journal of the American Chemical Society》2003,125(37):11150-11151
The hydroxylase component (MMOH) of soluble methane monooxygenase from Methylococcus capsulatus (Bath) was reduced to the diiron(II) form and then allowed to react with dioxygen to generate the diiron(IV) intermediate Q in the first phase of a double-mixing stopped-flow experiment. CD3NO2 was then introduced in the second phase of the experiment, which was carried out in D2O at 25 degrees C. The kinetics of the reaction of the substrate with Q were monitored by stopped-flow Fourier transform infrared spectroscopy, observing the disappearance of the asymmetric NO2 bending vibration at 1548 cm-1. The data were fit to a single-exponential function, which yielded a kobs of 0.45 +/- 0.07 s-1. This result is in quantitative agreement with a kobs of 0.39 +/- 0.01 s-1 obtained by observing the disappearance of Q by double-mixing stopped-flow optical spectroscopy at its absorption maximum of 420 nm. These results provide for the first time direct monitoring of the hydroxylation of a methane-derived substrate in the MMOH reaction pathway and demonstrate that Q decay occurs concomitantly with substrate consumption. 相似文献
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Tandem reaction of α-diazocarbonyl compounds in the presence of rhodium(II) acetate catalyst is described to furnish a range of conformationally restricted C2 symmetric macrodiolides via head to tail dimerization of intramolecular carbonyl ylides. 相似文献
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Reported herein is an intramolecular 1,3-dipolar cycloaddition strategy for rapid entry into benzopyranopyrazoles (BPP) on water medium as “open flask chemistry” approach. The in situ generation of diazo functionality in two-step sequence from the appropriate alkylated salicylaldehydes undergoes smooth [3?+?2]-cycloaddition with unactivated alkynes/alkenes furnishing benzopyranopyrazoles in good yield. This methodology was also extended for the synthesis of pyrazole incorporated macrocycles. This cascade protocol involving water medium provides an atom-economical and environment friendly approach. 相似文献
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G. Muthusamy P. Viswanathamurthi M. Muthukumar K. Natarajan 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):2115-2124
Several new hexa-coordinated ruthenium(II) and penta-coordinated rhodium(I) complexes of the types [RuCl(CO)(PPh 3 ) 2 (TSC)], [RuH(CO)(PPh 3 ) 2 (TSC)], and [Rh(PPh 3 ) 3 (TSC)] (where TSC = anion of thiosemicarbazone Schiff bases) have been prepared by the reactions of [RuHCl(CO)(PPh 3 ) 3 ], [RuH 2 (CO)(PPh 3 ) 3 )], and [RhH(PPh 3 ) 4 ] with thiosemicarbazones of 2-furaldehyde (H-FTSC), thiophene-2-carboxaldehyde (H-TCTSC), p-anisaldehyde (H-ATSC), piperonaldehyde (H-PTSC), and cyclohexanone (H-CTSC). All the new complexes obtained have been characterized on the basis of elemental analysis, IR, 1 H NMR, 31 P NMR, and electronic spectral data. 相似文献
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Synthesis of conformationally restricted dispiro- and bis-dispiro-1,3-dioxolanes via three-component reaction of diazoamides, ketoamides/diketones, and aromatic/heteroaromatic aldehydes in the presence of rhodium(II) acetate dimer catalyst at room temperature involving carbonyl ylides is demonstrated with diastereoselectivity. Synthesis of macrocyclic dispiro-1,3-dioxolanes via intramolecular carbonyl ylide is also delineated in high yield. The conformationally restricted symmetrical as well as unsymmetrical dispiro-1,3-dioxolanes were obtained under mild conditions in a highly diastereo- and regioselective manner. 相似文献
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l-Glutamine amidohydrolase (l-glutaminase, EC 3.5.1.2) is a therapeutically and industrially important enzyme. Because it is a potent antileukemic agent
and a flavor-enhancing agent used in the food industry, many researchers have focused their attention on l-glutaminase. In this article, we report the continuous production of extracellular l-glutaminase by the marine fungus Beauveria bassiana BTMF S-10 in a packed-bed reactor. Parameters influencing bead production and performance under batch mode were optimized
in the order-support (Na-alginate) concentration, concentration of CaCl2 for bead preparation, curing time of beads, spore inoculum concentration, activation time, initial pH of enzyme production
medium, temperature of incubation, and retention time. Parameters optimized under batch mode for l-glutaminase production were incorporated into the continuous production studies. Beads with 12×108 spores/g of beads were activated in a solution of 1% glutamine in seawater for 15 h, and the activated beads were packed
into a packed-bed reactor. Enzyme production medium (pH 9.0) was pumped through the bed, and the effluent was collected from
the top of the column. The effect of flow rate of the medium, substrate concentration, aeration, and bed height on continuous
production of l-glutaminase was studied. Production was monitored for 5 h in each case, and the volumetric productivity was calculated. Under
the optimized conditions for continuous production, the reactor gave a volumetric productivity of 4.048 U/(mL·h), which indicates
that continuous production of the enzyme by Ca-alginate-immobilized spores is well suited for B. bassiana and results in a higher yield of enzyme within a shorter time. The results indicate the scope of utilizing immobilized B. bassiana for continuous commercial production of l-glutaminase. 相似文献
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