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81.
82.
A concise synthesis of maremycins A and D1 has been accomplished via cycloaddition of a chiral cyclic nitrone with ( E)-3-ethylidene-1-methylindolin-2-one as a key step. This synthesis clarifies the stereochemistry of the maremycins and is suitable for large-scale synthesis for biological screening. 相似文献
83.
Terumichi Enomoto Mifuyu Ueno Yumi Shimada Ryuichi Shirai Kiyomi Kakiuchi 《Tetrahedron》2008,64(18):4051-4059
We report here on the construction of the ABC-ring framework of (±)-Taxol using an intramolecular aldol reaction as a key step. AB-ring compound 8 was converted to ketoaldehyde 25 as a precursor of an aldol reaction via introduction of oxygen-functionalities and a methoxycarbonyl group, which can be converted to a methyl group, in the proper positions of the B-ring. An aldol reaction of ketoaldehyde with LDA led to the formation of the desired product 27, which corresponds to the ABC-ring framework of (±)-Taxol. 相似文献
84.
Binding energies of selected hydrogen bonded complexes have been calculated within the framework of density functional theory (DFT) method to discuss the efficiency of numerical basis sets implemented in the DFT code DMol3 in comparison with Gaussian basis sets. The corrections of basis set superposition error (BSSE) are evaluated by means of counterpoise method. Two kinds of different numerical basis sets in size are examined; the size of the one is comparable to Gaussian double zeta plus polarization function basis set (DNP), and that of the other is comparable to triple zeta plus double polarization functions basis set (TNDP). We have confirmed that the magnitudes of BSSE in these numerical basis sets are comparative to or smaller than those in Gaussian basis sets whose sizes are much larger than the corresponding numerical basis sets; the BSSE corrections in DNP are less than those in the Gaussian 6-311+G(3df,2pd) basis set, and those in TNDP are comparable to those in the substantially large scale Gaussian basis set aug-cc-pVTZ. The differences in counterpoise corrected binding energies between calculated using DNP and calculated using aug-cc-pVTZ are less than 9 kJ/mol for all of the complexes studied in the present work. The present results have shown that the cost effectiveness in the numerical basis sets in DMol3 is superior to that in Gaussian basis sets in terms of accuracy per computational cost. 相似文献
85.
Henares TG Funano S Terabe S Mizutani F Sekizawa R Hisamoto H 《Analytica chimica acta》2007,590(2):173-179
Gastrodin is a bioactive constituent of rhizome in Gastrodia elata Blume (Orchidaceae) The aim of this study is to develop a rapid and sensitive liquid chromatographic method coupled to microdialysis sampling system to measure the unbound of gastrodin in rat blood, brain and bile. Microdialysis probes were simultaneously inserted into the jugular vein, brain striatum and bile duct of each anesthetized rat for sampling after the administration of gastrodin (100 or 300 mg kg−1) through the femoral vein. Separation of unbound gastrodin from various biological fluids was applied to an RP-select B column (250 mm × 4.6 mm i.d., 5 μm). The mobile phase consisted of acetonitrile–50 mM potassium dihydrogen phosphate buffer–triethylamine (5:95:0.1, v/v/v, adjusted to pH 2.5 with orthophosphoric acid) with a flow rate of 1 mL min−1. The UV detector wavelength was set at 221 nm. Fifteen minutes after the administration, the gastrodin reached the peak concentration in brain and bile. In addition, the results indicate that gastrodin penetrates the blood-brain barrier (BBB) and goes through hepatobiliary excretion. 相似文献
86.
Jubilut GN Cilli EM Crusca E Silva EH Okada Y Nakaie CR 《Chemical & pharmaceutical bulletin》2007,55(3):468-470
Based on our studies of the stability of model peptide-resin linkage in acid media, we previously proposed a rule for resin selection and a final cleavage protocol applicable to the Nalpha-tert-butyloxycarbonyl (Boc)-peptide synthesis strategy. We found that incorrect choices resulted in decreases in the final synthesis yield, which is highly dependent on the peptide sequence, of as high as 30%. The present paper continues along this line of research but examines the Nalpha-9-fluorenylmethyloxycarbonyl (Fmoc)-synthesis strategy. The vasoactive peptide angiotensin II (AII, DRVYIHPF) and its [Gly8]-AII analogue were selected as model peptide resins. Variations in parameters such as the type of spacer group (linker) between the peptide backbone and the resin, as well as in the final acid cleavage protocol, were evaluated. The same methodology employed for the Boc strategy was used in order to establish rules for selection of the most appropriate linker-resin conjugate or of the peptide cleavage method, depending on the sequence to be assembled. The results obtained after treatment with four cleavage solutions and with four types of linker groups indicate that, irrespective of the circumstance, it is not possible to achieve complete removal of the peptide chains from the resin. Moreover, the Phe-attaching peptide at the C-terminal yielded far less cleavage (50-60%) than that observed with the Gly-bearing sequences at the same position (70-90%). Lastly, the fastest cleavage occurred with reagent K acid treatment and when the peptide was attached to the Wang resin. 相似文献
87.
88.
89.
Lipase‐catalyzed regioselective polymerization of divinyl sebacate and triols has been performed in bulk. NMR analysis of the product obtained by the polymerization of divinyl sebacate and glycerol using Candida antarctica lipase at 60°C showed that 1,3‐diglyceride was a main unit and a small amount of the branching unit (triglyceride) was contained. The polymerization of divinyl sebacate with 1,2,4‐butanetriol or 1,2,6‐hexanetriol at 60°C produced a branched polymer. In polymerization at a lower temperature, the regioselectivity was perfectly controlled to give a linear polymer consisting of the α,ω‐disubstituted unit exclusively. The lipase origin and feed ratio of monomers greatly affected the microstructure of the polymer; under selected conditions, regiospecific polymerization was achieved. 相似文献
90.