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1.
Ramon Rios 《Tetrahedron letters》2006,47(48):8547-8551
A highly enantioselective catalytic asymmetric synthesis of 2H-1-benzothiopyrans is presented. The organocatalytic asymmetric domino reactions between 2-mercaptobenzaldehyde and α,β-unsaturated aldehydes proceed with excellent chemo- and enantioselectivities to give the corresponding pharmaceutically valuable benzothiopyrans in high yields with 91-98% ee. 相似文献
2.
The structure elucidation and 1H and 13C assignments of the new triterpenes 3beta-palmitoxy-7beta-hydroxyolean-12-ene (1) and its hydrolysis product 3beta,7beta-dihydroxyolean-12-ene (2) and 3beta-sn-glyceroyl-(1'-palmitoxy)urs-12-ene (3), isolated from the aerial parts of Cladocolea grahami (Loranthaceae), are reported. 相似文献
3.
Treatment of ethyl 2-(pyridin-2-ylsulfonyl)hexanoate with tributylstannane and azobis(2-methyl-2-propanitrile) (AIBN) in benzene at reflux for 36 h resulted in hydrogenolysis to give ethyl hexanoate (60%), whereas no reaction was observed after 48 h at reflux with ethyl 2-(phenylsulfonyl)hexanoate. Ethyl 2-(pyrimidin-2-ylsulfonyl)hexanoate underwent quantitative hydrogenolysis within 1 h under these conditions. This represents a mild new methodology for removal of the synthetically useful sulfone moiety. Substitution of Bu(3)SnD for Bu(3)SnH gave access to alpha-deuterium-labeled esters. Treatment of the alpha-(pyrimidin-2-ylsulfonyl) enolates derived from several esters with Selectfluor gave high yields of the 2-fluoro-2-(pyrimidin-2-ylsulfonyl)alkanoates, which were smoothly desulfonylated [Bu(3)SnH (2 equiv)/AIBN/benzene/Delta] to give 2-fluoroalkanoates. "Catalytic" tin hydride, generated from tribuytltin chloride (0.15 equiv) and excess polymethylhydrosiloxane in the presence of potassium fluoride, also effected removal of the pi-deficient alpha-(pyrimidin-2-ylsulfonyl) moiety from acid derivatives in high yields. Desulfonylation is suggested to proceed via alkoxy ketyl-type radicals and tin enolates. 相似文献
4.
White-Morris RL Stender M Tinti DS Balch AL Rios D Attar S 《Inorganic chemistry》2003,42(10):3237-3244
The preparation and X-ray crystal structures of (CyNC)Au(I)CN, (n-BuNC)Au(I)CN, and (i-PrNC)Au(I)CN.0.5CH(2)Cl(2) are reported and compared with those of (MeNC)Au(I)CN and (t-BuNC)Au(I)CN, which were previously described. These linear molecules are all organized through aurophilic interactions into three structural classes: simple chains ((CyNC)Au(I)CN and (t-BuNC)Au(I)CN), side-by-side chains in which two strands make Au...Au contact with each other ((n-BuNC)Au(I)CN), and nets in which multiple aurophilic interactions produce layers of gold(I) centers ((i-PrNC)Au(I)CN and (MeNC)Au(I)CN). All of these five solids dissolve to produce colorless, nonluminescent solutions with similar UV/vis spectra. However, each of the solids displays a unique luminescence with emission maxima occurring in the range 371-430 nm. 相似文献
5.
Rios R Jimeno C Carroll PJ Walsh PJ 《Journal of the American Chemical Society》2002,124(35):10272-10273
We have demonstrated the feasibility of the kinetic resolution of atropisomeric amides using the commercially avaliable AD-mix. To our knowledge, this methodology represents the first catalytic kinetic resolution of such compounds. Relative rates of up to 32 have been found for the kinetic resolution processes. We have also determined the barriers to rotation and half-lives of some of these amides. The half-lives range from 7 to 135 h at room temperature. 相似文献
6.
Determination of rate constants and reaction orders with an open-closed flow-injection configuration
A new, very useful application of open-closed configurations to kinetic studies is reported. The multipeak recordings provided by the manifold used, which features a single conventional photometric detector, were used to calculate the rate constants and reaction orders of a chemical system, namely the ligand displacement reaction between the cobalt(II)-EGTA complex and PAR. 相似文献
7.
Crystallographic and luminescence studies on salts of the two-coordinate carbene cation, [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)](+), demonstrate the ability of the cation to exist in three different states of aggregation. In colorless, non-luminescent [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)]Cl the cation crystallizes as a monomer with the nearest gold(i) center 6.7890(11) A away. Colorless, luminescent [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)]AsF(6) forms dimers with an AuAu separation of 3.1288(4) A. These dimers form weakly associated extended chains of cations with additional AuAu separations of 3.6625(5) A. [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)]PF(6) is isostructural. Yellow, luminescent [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)](3)(AsF(6))(2)Cl.0.5(H(2)O)(2) and [Au{C(NHCH(3))(NHCH(2)CH(2)OH)}(2)](3)(PF(6))(2)Cl.0.5(H(2)O)(2) form trimers that further aggregate into extended chains with rather short AuAu separations of 3.1301(14) A, 3.1569(14) A and 3.1415(14) A. Absorption, emission and excitation spectra are reported for these salts. The excitation and emission results from the interactions between the gold centers and involves transitions between the filled d(z)((2)) band and the empty p(z) bands with the z axis pointing along the chain of cations. 相似文献
8.
Crugeiras J Rios A Riveiros E Amyes TL Richard JP 《Journal of the American Chemical Society》2008,130(6):2041-2050
Equilibrium constants in D2O were determined by 1H NMR analyses for formation of imines/iminium ions from addition of glycine methyl ester to acetone and from addition of glycine to phenylglyoxylate. First-order rate constants, also determined by 1H NMR, are reported for deuterium exchange between solvent D2O and the alpha-amino carbon of glycine methyl ester and glycine in the presence of increasing concentrations of ketone and Br?nsted bases. These rate and equilibrium data were used to calculate second-order rate constants for deprotonation by DO- and by Br?nsted bases of the alpha-imino carbon of the ketone adducts. Formation of the iminium ion between acetone and glycine methyl ester and between phenylglyoxylate and glycine is estimated to cause 7 unit and 15 unit decreases, respectively, in the pKa's of 21 and 29 for deprotonation of the parent carbon acids. The effect of formation of iminium ions to phenylglyoxylate and to 5'-deoxypyridoxal (DPL) [Toth, K.; Richard, J. P. J. Am. Chem. Soc. 2007, 129, 3013-3021] on the carbon acidity of glycine is similar. However, DPL is a much better catalyst than phenylglyoxylate of deprotonation of glycine, because of the exceptionally large thermodynamic driving force for conversion of the amino acid and DPL to the reactive iminium ion. 相似文献
9.
Ramon Rios 《Tetrahedron letters》2007,48(32):5701-5705
The highly chemo- and enantioselective organocatalytic three-component reaction between N-arylhydroxylamines, aldehydes and α,β-unsaturated aldehydes is presented; the reaction gives access to isoxazolidines in high yields with >25:1 dr and 91-99% ee. 相似文献
10.
Hidalgo C Rios C Hidalgo M Salvadó V Sancho JV Hernández F 《Journal of chromatography. A》2004,1035(1):153-157
An existing method for the determination of glyphosate and its main metabolite aminomethylphosphonic acid (AMPA) in water has been improved. It is based on precolumn derivatization with the fluorescent reagent 9-fluorenylmethylcloroformate (FMOC) followed by large-volume injection in a coupled-column LC system using fluorescence detection (LC-LC-FD). The derivatization step was slightly modified by changing parameters such as volume and/or concentration of sample and reagents to decrease the limits of quantification (LOQ) of glyphosate and AMPA to 0.1 microg/l. Additionally, the use of Amberlite IRA-900 for preconcentration of glyphosate, prior to the derivatization step, was investigated; the LOQ of glyphosate was lowered to 0.02 microg/l. Drinking, surface and ground water spiked with glyphosate and AMPA at 0.1-10 microg/l concentrations were analysed by the improved LC-LC-FD method. Recoveries were 87-106% with relative standard deviations lower than 8%. Drinking and ground water spiked with glyphosate at 0.02 and 0.1 microg/l were analysed after preconcentration on the anion-exchange resin with satisfactory recoveries (94-105%) and precision (better than 8%). 相似文献