The ruthenium-catalysed double addition of trimethylsilyldiazomethane to alkynes developed by Dixneuf and co-workers was applied to the synthesis of 2-alkyl- or 2-aryl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,4-bis(trimethylsilyl)-1,3-butadienes by use of alkynylboronates instead of alkynes. Di- and tetrasubstituted 1,3-butadienes were prepared from a 2-boryl-1,4-disilyl-1,3-butadiene, using the Suzuki-Miyaura coupling reaction, iodolysis of the alkenylsilane moieties with N-iodosuccinimide and hydrolysis of the carbon-silicon bonds with trifluoroacetic acid. The same compound was converted also to a bicyclic compound, a trisubstituted 1,3-butadiene and a dienone through the Diels-Alder reaction, oxidation of the alkenylboronate moiety and the Mukaiyama aldol reaction. 相似文献
The ring conformation of 2-O-methyl-1,3,4,5-tetrakis-O-tert-butyldiphenylsilyl-myo-inositol was in a twist form both in solid state and in solution. This is the first observation of a stable twist conformer induced by the introduction of bulky silyl protecting groups. 相似文献
A novel self-oscillating polymer was prepared by utilizing the Belousov-Zhabotinsky (BZ) reaction. In this study, a sulfonic acid group was newly introduced as a pH-control site into the copolymer of N-isopropylacrylamide, and the ruthenium complex was introduced as a catalyst site. By introducing the pH-control site, we succeed in causing the soluble-insoluble self-oscillation of the polymer solution under acid-free conditions in which only two BZ substrates, malonic acid and sodium bromate, were present as added agents. The self-oscillating behavior was remarkably influenced by the temperature and polymer concentration, which reflects the intermolecular aggregative capacity of the polymer chains in the reduced state to change the lower critical solution temperature. This achievement of self-oscillation of polymer chains under acid-free conditions may lead to their practical use as novel biomimetic materials under biological conditions. 相似文献
Diethyl bromodifluoromethyl phosphonate reacts readily with cadmium metal to form a stable cadmium complex. Depending on solvent, this functionalized organocadmium reagent exhibits stability for days to months. It reacts with a variety of electrophiles and serves as a synthetically useful source for the introduction of the difluoromethylene phosphonate group into organic compounds.The synthetic utility of a wide variety of fluoromethylene phosphonium ylides has been a major effort in our laboratory over the past several years [1]. The generation and capture of difluoromethylene ylides () as a general route to difluoromethylene olefins has been of especial interest to us [2]. In an effort to increase the nucleophilicity of the ylide, we have attempted to prepare the analogous phosphonate ylide (). Although we have achieved modest success [3] by capture of () in the reaction of sodium dialkyl phosphites with diethyl bromodifluoromethylphosphonate (), attempts to pregenerate (), either from diethyl difluoromethylphosphonate () or (), have met with little success. () appears to have minimal stability even at low temperatures, and scale up processes of synthetic value would seem to be difficult. 相似文献
Summary Alumina may be considerably modified by impregnating at 100°C in the alkali metal phosphate solution. The available solution for modification was the KOH–K2HPO4–AlPO4 (11.51M) solution or the NaOH–Na2 HPO4 (0.81.1 M or 11.5M) solution. The appreciable improvement on chromatograms was obtained by preheating of the alumina, especially above 800°C prior to impregnating A further modification may be made by ignition of the alumina impregnated. The x-ray diffraction studies revealed the phase transformation of the alumina inducing the modification, and the essential factor of the present modification method being the thermal treatment of the alumina at temperatures forming -alumina. 相似文献
A palladium-indium triflate catalyst was found to be much more active for the dimerization of vinylarenes compared with generally used cationic palladium(II) catalysts. 相似文献
The Mössbauer spectra of Sm2Fe17Nx, prepared by the nitrogenation of Sm2Fe17 powders in an ammonia and hydrogen atmosphere, were observed at elevated temperatures to shed light on the thermal behavior of nitrogen in the compounds Sm2Fe17Nx. It was found that there were large differences in thermal behavior between the starting Sm2Fe17, crystalline Sm2Fe17Nx (x≈1.7) and amorphous Sm2Fe17Nx(x~7). The thermal decomposition behavior of Sm2Fe17N3.2, developed as one of the most promising hard magnetic materials, was found to be different under different atmospheres. 相似文献
In an effort to develop an efficient synthetic method of highly diastereoselective (2′R)- and (2′S)-2′-deoxy[2′-2H]guanosines, chemoenzymatic conversion was investigated. The synthesis of (2′R > 98% de)-2′-deoxy[2′-2H]guanosine was achieved by biological transdeoxyribosylation using (2′R > 98% de)-2′-deoxy[2′-2H]uridine, 2,6-diaminopurine, and Enterobacter aerogenes AJ-11125, followed by treatment with adenosine deaminase. (2′S > 98% de)-2′-Deoxy[2′-2H]guanosine was synthesized from (2′S > 98% de)-2′-deoxy[2′-2H]uridine and 2,6-diaminopurine using thymidine phosphorylase and purine nucleoside phosphorylase instead of E. aerogenes AJ-11125. 相似文献
Two novel palladium(0)-catalyzed cyclizations of allenenes are described. Treatment of allenenes such as N-(1-alkyl-2,3-butadienyl)-N-allylsulfonamide with an aryl halide and K(2)CO(3) in the presence of a catalytic amount of Pd(PPh(3))(4) in dioxane affords 2,3-cis-pyrrolidines in a stereoselective manner. In sharp contrast, cyclization of the same allenenes using catalytic Pd(2)(dba)(3) x CHCl(3) in the presence of allyl methyl carbonate in CH(3)CN leads to stereoselective formation of a 3-azabicyclo[3.1.0]hexane framework in moderate yields. 相似文献