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31.
32.
A bioassay-directed fractionation of the cytotoxic constituents of the Japanese sea hare Dolabella auricularia resulted in the isolation of two 35-membered depsipeptides dolastatin G (1) and nordolastatin G (2), which showed cytotoxicity against HeLa S(3) cells with IC(50) values of 1.0 and 5.3 &mgr;g/mL, respectively. The gross structures of these substances were established by spectroscopic analysis including 2D NMR techniques. The absolute stereostructure of 1 was determined by chiral HPLC analysis of amino acid components obtained from acid hydrolysis of 1 and by the enantioselective syntheses of two degradation products arising from polyketide portions. Nordolastatin G (2) is a congener that has the same absolute stereochemistry as that of 1. 相似文献
33.
Miura T Goto K Waragai H Matsumoto H Hirose Y Ohmae M Ishida HK Satoh A Inazu T 《The Journal of organic chemistry》2004,69(16):5348-5353
The Bfp-OH, a novel fluorous protecting reagent, was able to be easily prepared. The Bfp group was readily introduced to a carbohydrate, removed in high yield, and recyclable after cleavage. The use of the Bfp group made it possible to synthesize a pentasaccharide by minimal column chromatography purification. Each synthetic intermediate was able to be easily purified only by simple fluorous-organic solvent extraction and monitored by TLC, NMR, and MS. 相似文献
34.
Rapid synthesis of oligosaccharide moieties of globotriaosylceramide using fluorous protective group
Tsuyoshi MiuraToshiyuki Inazu 《Tetrahedron letters》2003,44(9):1819-1821
The use of the Bfp (bisfluorous chain type propanoyl) group as a fluorous protective group made it possible to rapidly synthesize galabiose and the Gb3 oligosaccharide derivatives by a simple fluorous-organic extraction purification. The fluorous oligosaccharide synthesis using the Bfp group is an excellent strategic alternative to solid phase oligosaccharide synthesis, and removes some of the disadvantages of the solid phase method. 相似文献
35.
Treatment of magnesium alkylidene carbenoids, generated from 1-chlorovinyl p-tolyl sulfoxides with isopropylmagnesium chloride at −78 °C in toluene, with 2-lithiothiophenes gave 2-alkenylated thiophenes in good to high yields. The intermediate of this reaction was found to be an alkenylmagnesium, which could be trapped with iodoalkanes and ethyl chloroformate. This procedure offers a novel and efficient one-pot synthesis of thiophenes having a disubstituted or a trisubstituted olefin at the 2-position from thiophenes in good yields. 相似文献
36.
Masao Matsuoka Tsuyoshi Matsuda June Tamaki Yoshifumi Yamamoto Chiaki Iwakura 《Research on Chemical Intermediates》2006,32(5):389-402
Laves-phase hydrogen storage alloy has a high potential for use as negative electrode material as alternative for the misch-metal-based
material. In order to improve the energy density and the rate capability of negative electrode, chemical and mechanical modification
of Lavesphase alloy with different stoichiometric ratios was carried out. Discharge capacity and high-rate dischargeabilty
was evaluated by electrochemical methods and the characterization of Laves-phase alloy was made by X-ray diffraction, SEM
observation and PCT measurement. The best result in discharge capacity could be obtained for stoichiometric Laves-phase alloy
with a composition of Zr0.9Ti0.1Ni1.1Co0.1Mn0.5V0.2Cr0.1 by boiling in 10 M KOH solution. On the other hand, the high-rate dischargeability was increased remarkably by introducing
mechanical grinding before alkali treatment. The cause for improved performance was discussed on the basis of thermodynamic
stability of metal hydride and changes in crystal structure and surface morphology influencing on diffusion coefficient and
diffusion path length of hydrogen. 相似文献
37.
Yan H Sato T Komago D Yamaguchi A Oyaizu K Yuasa M Otake K 《Langmuir : the ACS journal of surfaces and colloids》2005,21(26):12303-12308
A conductive polypyrrole (PPy) film was successfully synthesized in a homogeneous supercritical carbon dioxide (scCO2)/acetonitrile (AN) system. The occurrence of a homogeneous supercritical state was confirmed by observations of the phase behavior of the system through a high-pressure cell with a viewing window. The concentration of a supporting electrolyte, tetrabutylammonium hexafluorophosphate (TBAPF6), significantly changed the phase behavior of the scCO2/AN system. The polymerization rate of the film in that system decreased with further addition of CO2. This result suggested that the low viscosity of scCO2 did not play an important role in improving the growth rate of the PPy film. The low polymerization rate might have been due to the electron-transfer resistance arising from the low dielectric constant of scCO2/AN mixture. The roughness of the film prepared in the homogeneous scCO2/AN system was 1/10 that synthesized in AN itself as a solvent. The slow growth of film and the high diffusion rate of the monomer seemed to account for the smooth flat film formation. 相似文献
38.
Treatment of 1-chlorovinyl p-tolyl sulfoxides, prepared from ketones and chloromethyl p-tolyl sulfoxide, with N-lithio arylamines resulted in the formation of sulfinylaziridines in good to high yields. The sulfinylaziridines were treated with N-lithio aniline or N-lithio p-chloroaniline to afford α-quaternary α-amino aldehydes in good yields. From α-quaternary α-amino aldehydes, α-quaternary α-amino acid esters and β-quaternary β-amino alcohols were obtained. When optically active chloromethyl p-tolyl sulfoxide was used in this procedure, a method for the synthesis of optically active α-quaternary α-amino aldehydes was realized. The reaction mechanism, including asymmetric induction, for the formation of the sulfinylaziridines is described. 相似文献
39.
1-Chlorovinyl p-tolyl sulfoxides were synthesized from several kinds of cyclic ketones and chloromethyl p-tolyl sulfoxide in good yields. Treatment of the 1-chlorovinyl p-tolyl sulfoxides with cyanomethyllithium at −78°C to room temperature gave spirocyclic enaminonitriles in high yields. Acidic treatment of the enaminonitriles afforded spiro[4.n]alkenones in good yields. By using an unsymmetrical cyclic ketone, α-tetralone, and optically active chloromethyl p-tolyl sulfoxide, this procedure afforded enantiomerically pure spiro[4.5]decenone in good yield with excellent asymmetric induction from the sulfoxide chiral center. By using this method a formal total synthesis of a racemic spirocyclic sesquiterpene, acorone, was realized. 相似文献
40.
Furusho Y Oku T Hasegawa T Tsuboi A Kihara N Takata T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(12):2895-2903
A dynamic covalent approach to disulfide-containing [2]- and [3]rotaxanes is described. Symmetrical dumbbell-shaped compounds with two secondary ammonium centers and a central located disulfide bond were synthesized as components of rotaxanes. The rotaxanes were synthesized from the dumbbell-shaped compounds and dibenzo-[24]crown-8 (DB24C8) with catalysis by benzenethiol. The yields of isolated rotaxanes reached about 90 % under optimized conditions. A kinetic study on the reaction forming [2]rotaxane 2 a and [3]rotaxane 3 a suggested a plausible reaction mechanism comprising several steps, including 1) initiation, 2) [2]rotaxane formation, and 3) [3]rotaxane formation. The whole reaction was found to be reversible in the presence of thiols, and thermodynamic control over product distribution was thus possible by varying the temperature, solvent, initial ratio of substrates, and concentration. The steric bulk of the end-capping groups had almost no influence on rotaxane yields, but the structure of the thiol was crucial for reaction rates. Amines and phosphines were also effective as catalysts. The structural characterization of the rotaxanes included an X-ray crystallographic study on [3]rotaxane 3 a. 相似文献