Lipase TL-mediated kinetic resolution of (+/-)-5-benzyloxy-1-tert-butyldimethylsilyloxy-2-pentanol (5) at low temperature proceeded to give the corresponding (S)-alcohol 5 and (R)-acetate 6 in quantitative yields with high enantiomeric purity. The addition of bases such as pyridine, DMAP, 2,4- and 2,6-lutidines, or triethylamine considerably enhanced the rate of kinetic resolution. The alcohol (S)-5 and the acetate (R)-6 were converted to piperazic acid derivatives (R)- and (S)-3, respectively, via the intramolecular Mitsunobu reaction as a key step. 相似文献
Multiple internal reflection infrared spectroscopy was applied to in situ investigations of surface intermediates of photocatalytic reactions on nanocrystalline TiO(2) films in contact with aqueous solutions. UV irradiation in the presence of dissolved O(2) caused the appearance of new bands peaked at 943, 838, and 1250-1120 cm(-)(1) together with intensity changes in other bands. Investigations of influences of the solution pH, the presence or absence of hole and electron scavengers, and isotopic H(2)O --> D(2)O exchange on the spectral changes have revealed that the primary step of photocatalytic O(2) reduction is the formation of the surface peroxo species, Ti(O(2)), giving the 943 cm(-)(1) band, probably with the surface superoxo species, TiOO., as a precursor, in neutral and acidic solutions. The surface peroxo species is then transformed to the surface hydroperoxo, TiOOH, giving the 838 and 1250-1120 cm(-)(1) bands, by protonation in the dark. This is, to our knowledge, the first direct in situ spectroscopic detection of primary intermediates for the photocatalytic O(2) reduction in aqueous solutions. On the basis of the assignment, a possible reaction scheme for various processes of the photocatalytic O(2) reduction is proposed, which is in harmony with other spectral changes induced by the UV irradiation. 相似文献
We derive the macroscopic laws that govern the evolution of the density of particles in the exclusion process on the Sierpinski gasket in the presence of a variable speed boundary. We obtain, at the hydrodynamics level, the heat equation evolving on the Sierpinski gasket with either Dirichlet or Neumann boundary conditions, depending on whether the reservoirs are fast or slow. For a particular strength of the boundary dynamics we obtain linear Robin boundary conditions. As for the fluctuations, we prove that, when starting from the stationary measure, namely the product Bernoulli measure in the equilibrium setting, they are governed by Ornstein-Uhlenbeck processes with the respective boundary conditions.
Carboxylic acids were heated at 150 °C in DMF in the presence of 1.25 equiv of thionyl chloride to give corresponding N,N-dimethylamides in good yields. Tandem chlorination and amidation reactions occurred in the one-pot procedure. Dicarboxylic acids needed prolonged reaction time to produce bisamides in good yields. Some benzamides were efficiently converted into corresponding 1,2-diaryl-1,2-diketones (benzils) under acyloin condensation conditions in the presence of 4,4′-di-tert-butylbiphenyl (DBB) in THF. Ultrasonic irradiation effectively accelerates the reaction, but it is not critical. However, the presence of DBB is fatal to the reaction. Although a few synthetic methods for benzils from benzoic acids have been reported so far, this method is one of the most convenient and highly reproducible procedures. 相似文献
The reaction of 1-chlorovinyl p-tolyl sulfoxides, which were derived from ketones and chloromethyl p-tolyl sulfoxide, with lithium acetylides gave adducts in moderate to good yields. Treatment of the adducts with Grignard reagents resulted in the formation of magnesium carbenoids by the sulfoxide-magnesium exchange reaction. 1,2-Carbon-carbon insertion (1,2-CC insertion) reaction of the generated magnesium carbenoids took place to afford conjugated enynes in good to high yields. This procedure provides a good method for the synthesis of multi-substituted conjugated enynes. 相似文献
This paper presents the decomposition by-products of trifluro-iodo-methane and their relative proportions in the gas phase under the occurrence of partial discharge. The experiment was performed in the presence of water vapor from 250 to 400 ppm under a non-uniform electric field configuration. The experimental results reveal that the by-products of C2F6, C2F4, C2F5I with the amount of 1300, 200, and 55 (CH3I) ppm, respectively, were produced for a cumulative charge of 161 mC. Other by-products, such as C3F8, CHF3, C3F6 CH3I were obtained at less than 30 ppm C2F6 was the dominant gas by-product of trifluro-iodo-methane suffering partial discharge. 相似文献