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941.
Three different procedures are compared to obtain properly substituted divinyl ketones in which one of the double bonds is embedded in a five-membered heterocyclic structure and therefore suitable to produce cyclopenta-fused pyrrole derivatives by the acid-catalyzed Nazarov reaction. These, on treatment with TFA, afforded 2,4-cis-disubstituted 2,3,4,5-tetrahydro-1H-cyclopenta[b]pyrrol-6-ones with high stereocontrol. One of these Nazarov products was oxidized to the corresponding 4,5-dihydro-1H-cyclopenta[b]pyrrol-6-one derivative, thus obtaining an enantiopure key intermediate in the total synthesis of roseophilin. 相似文献
942.
[Reaction: see text]. A collection of 13 unsymmetrical ketones, each one featuring a sugar (d-glucosyl, d-galactosyl, d-mannosyl, and l-fucosyl) and an aglycone moiety (phenyl, 2-thiazolyl, TMS-ethynyl, allyl, and 1-propenyl) was prepared by a uniform route based on the use of benzothiazole as a carbonyl group equivalent. Succinctly, C-glycosylbenzothiazoles readily prepared by addition of 2-lithiobenzothiazole to sugar lactones and deoxygenation, were subjected to a one-pot reaction sequence involving N-methylation of the heterocyclic ring by MeOTf, treatment of the N-methylbenzothiazolium salt with a Grignard reagent, and HgCl(2)-promoted hydrolysis of the benzothiazoline thus formed. The resulting ketones were isolated in yields varying from 35 to 80%. Treatment of the sugar ketones with various organometals containing the phenyl, 2-thiazolyl, TMS-ethynyl, or ethynyl group as a substituent afforded chiral tertiary alcohols. These addition reactions were highly stereoselective as observed by crude NMR analysis and isolation of a single epimer in high yield in each case examined. However, because of the complexity of the reagents involved, the stereochemical outcome of these reactions appears to be difficult to rationalize by simple classical steric models, thus, ab initio studies taking into account the role of the sugar fragment are advisable. An interesting synthetic elaboration of a propargylic alcohol containing the thiazole ring into a propargylic alcohol bearing the formyl and carboxylate groups is reported. 相似文献
943.
Arseniyadis S Subhash PV Valleix A Mathew SP Blackmond DG Wagner A Mioskowski C 《Journal of the American Chemical Society》2005,127(17):6138-6139
We have described a spectacular salt effect in the kinetic resolution of (+/-)-1-phenylethylamine, which leads to an increase in reactivity, high levels of selectivity, and a complete reversal of the stereoselectivity. By tuning the reaction conditions, we were able to increase the selectivity factor of (1S,2S)-1 to s = 115. 相似文献
944.
Ruth K Dinnebier RE Tönnes SW Alig E Sänger I Lerner HW Wagner M 《Chemical communications (Cambridge, England)》2005,(27):3442-3444
Solvent-free [LiCH2SMe]infinity forms a layer structure consisting of four- (Li2C2), five- (Li2CS2), and six-membered (Li2C2S2) rings in the solid state; the compound violently explodes upon heating to T=160+/-5 degrees C under an argon atmosphere. 相似文献
945.
946.
Tams Sznyi Antonello Cossidente Andrs Gcs Csaba Mengyn Alessandro Siciliano Zsuzsa Weiner 《组合设计杂志》2005,13(1):25-41
The size of large minimal blocking sets is bounded by the Bruen–Thas upper bound. The bound is sharp when q is a square. Here the bound is improved if q is a non‐square. On the other hand, we present some constructions of reasonably large minimal blocking sets in planes of non‐prime order. The construction can be regarded as a generalization of Buekenhout's construction of unitals. For example, if q is a cube, then our construction gives minimal blocking sets of size q4/3 + 1 or q4/3 + 2. Density results for the spectrum of minimal blocking sets in Galois planes of non‐prime order is also presented. The most attractive case is when q is a square, where we show that there is a minimal blocking set for any size from the interval . © 2004 Wiley Periodicals, Inc. J Combin Designs 13: 25–41, 2005. 相似文献
947.
Using a high-gain image intensifier and a pulsed discharge gap, electron avalanches are photographed by means of the light emitted as a result of excitation processes by electron impact accompanying ionisation. — Principle and sensitivity of the method are briefly discussed. Electron drift velocities in nitrogen are measured, and the range of mean energy of agitation of electrons is derived from the photographs taken. Preliminary data have also been obtained for argon. 相似文献
948.
949.
950.
The diffusion of sulfur in nickel oxide single crystals has been investigated over the temperature range from 1000 to 1250°C. The measured data were found to deviate markedly from the error function complement dependence for diffusion from a constant source. The deviation is attributed to the migration of sulfur by the “double mode simultaneous diffusion mechanism.” The faster mode diffusion is suggested to be via nickel vacancies, and the slower mode diffusion is suggested to be via oxygen vacancies. The diffusivities for faster mode are given by Df = 2.94 exp[? 86.6 kcal/RT] cm2 sec?1 and, the slower mode, Ds = 1.08 × 10?9 exp [?32.8 kcal/RT]cm2sec?1. 相似文献