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21.
Peroxisomicine A1 is a potentially antineoplastic compound isolated from the seeds of Karwinskia parvifolia. It is considered as a useful chemotype for the preparation of topoisomerase II targeted anticancer cells. Stereochemically, it is characterized by the presence of two stereocenters and a rotationally hindered and thus likewise stereogenic biaryl axis. In this contribution, the absolute configuration of peroxisomicine A1 and its epimer, peroxisomicine A2, was established by means of a five-step degradative procedure giving the respective R- and S-configured methyl 2-(2′-methyl-5′-oxotetrahydrofuryl)acetates. The configuration of the degradation product was obtained by means of optical rotation, 1H NMR analysis using a chiral displacement reagent, and by experimental and quantum chemical circular dichroism (CD) investigations. Based on the results obtained here and considering our previous work on the relative configuration at centers versus axis of these compounds, peroxisomicine A1 resulted to be the P,3S,3′S-isomer and peroxisomicine A2 the P,3R,3′S-isomer. 相似文献
22.
Immobilized sulfhydryl groups were prepared by partial thiolation of NH2-glass beads. The microenvironment of the immobilized SH groups was varied by different chemical modifications of neighboring
NH2 groups. Introduction of a strong charge in the surroundings of immobilized sulfhydryls results in their dramatic stabilization
against autooxidation. This effect is due to the salting of O2 from the surface microlayer of the thiolated beads. 相似文献
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A spectrophotometric method has been developed for the simultaneous determination ofo-cresol andm-cresol in water by reaction withp-aminophenol (PAP). Three different methodologies have been assayed; (i) batch analysis, after reaction in an alkaline medium in the presence of dissolved molecular oxygen as oxidizing agent, (ii) a stopped-flow procedure, carried out in the presence of KIO4 and (iii) a flow injection method based on the same approach. The batch procedure requires 22 min for the full development of colour witho-cresol and 12 min form-cresol. In the stopped-flow mode, using KIO4 and a reaction time of 12 min, better sensitivity can be obtained for both compounds and limits of detection of 10 g 1–1 foro-cresol and 30 g 1–1 form-cresol were found. The flow injection method has a lower sensitivity but permits more than 80 injections per hour. Based on the different maximum absorbance wavelengths obtained for the reaction products of PAP witho-cresol (614 nm) andm-cresol (632 nm), both compounds can be simultaneously determined in water samples and recoveries of 90 to 115% were found in spiked water samples of different types. 相似文献
26.
Shin Kamijo 《Tetrahedron letters》2006,47(32):5629-5632
Cyclic vinylogous triflate hemiacetals can serve as ‘synthetic equivalents’ for alkynyl aldehydes: treatment of a vinylogous triflate hemiacetal with excess amounts of Grignard reagents produces acyclic alkynyl alcohols in good to high yields. This transformation likely involves the Grob-type C-C bond cleaving fragmentation to form the alkynyl aldehyde in situ. Subsequent nucleophilic attack of the Grignard reagent furnishes secondary alkynols. Vinylogous triflate hemiacetals are easily prepared by DIBALH reduction of vinylogous acyl triflates, which are derived from cyclic 1,3-diketones. 相似文献
27.
Jeffrey Axten Jennifer Troy Peter Jiang Mendel Trachtman Charles W. Bock 《Structural chemistry》1994,5(2):99-108
Ab initio molecular orbital calculations are used to study the modified Schlenk equilibrium: 2RMgCl (RMgCl)2 MgR2 + MgCl2 Mg(Cl2)MgR2 with R=H and CH3. In the absence of any solvents, calculations indicate that the formation of the various possible bridged dimers (RMgCl)2 is substantially exothermic. However, using dimethylether as a model solvent, we show that the formation of the dimer (Me2O)(CH3)Mg(Cl2)Mg(CH3)(OMe2) is exothermic only when entropic effects are included. 相似文献
28.
Takeshi Takeda Koutaro Arai Hirohisa Shimokawa Akira Tsubouchi 《Tetrahedron letters》2005,46(5):775-778
Cyclopropanes were obtained by the titanocene(II)-promoted reaction of thioacetals with vinyl pivalate. It was also found that vinycyclopropanes were produced by a similar treatment of thioacetals with the titanocene(II) species in the presence of 1,3-dienes. 相似文献
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30.
Yoshiyuki Masui 《Tetrahedron letters》2004,45(9):1853-1856
The title N-alkoxycarbonyl- or N-aryloxycarbonyl-substituted sulfamides were synthesised in one-pot in efficient yields from chlorosulfonyl isocyanate (CSI), alcohols and aqueous (or dry) amines via the corresponding water-resistant intermediates, carboxysulfamoylammonium salts (Burgess-type reagents), which were generated in situ by the deactivation of the corresponding water-sensitive N-(chlorosulfonyl)carbamates with tertiary amines. 相似文献