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The stereoselective total synthesis of (-)-microcarpalide, a recently discovered 10-membered lactone of fungal origin displaying a remarkable disrupting action on actin microfilaments, was accomplished by using ring-closing metathesis (RCM) as the key step for the formation of the medium-sized ring. The diene ester required for the macrocyclization reaction was assembled via DCC-mediated esterification of two suitable partners, each bearing a terminal alkene group. The alcohol fragment was synthesized from n-bromohexane through a seven-step sequence entailing two consecutive stereoselective homologations of chiral boronic esters as strategic transformations for the sequential insertion of the two stereocentres with the final S absolute configuration, using (+)-pinanediol as the chiral director; final elaboration to the desired C(11) framework envisaged treatment with an allyl Grignard reagent and oxidative cleavage of the boronic scaffold. In contrast, the acidic fragment was prepared in ten steps from d-tartaric acid, whose C(4) backbone was elongated to the required C(7) skeleton by means of two distinct Swern-Wittig oxidation-homologation sequences. 相似文献
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A mild synthesis of vinyl halides and gem-dihalides using triphenyl phosphite-halogen-based reagents
Spaggiari A Vaccari D Davoli P Torre G Prati F 《The Journal of organic chemistry》2007,72(6):2216-2219
A new application of (PhO)3P-halogen-based reagents to the synthesis of vinyl halides and gem-dihalides is described. Vinyl halides were prepared in good to excellent yields from enolizable ketones, whereas aldehydes afforded the corresponding gem-dihalides. The halogenation proceeded smoothly under mild conditions. 相似文献
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Mathematical Notes - The Browder-Livesay invariants provide obstructions to the realization of elements of Wall groups by normal maps of closed manifolds. A generalization of the iterated... 相似文献
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This note is related to a nice short paper of M. Ochiai. We prove in a very fast way that the two-parameter family of Heegaard diagrams, constructed by Ochiai, encodes the genuine three-sphere. The result is obtained, up to isotopy, by using a sequence of only three moves in this order: a Whitehead–Zieschang reduction, a band sum and a cancellation of a handle. 相似文献
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Periodica Mathematica Hungarica - The goal of this paper is to give some theorems which relate to the problem of classifying combinatorial (resp. smooth) closed 5-manifolds up to piecewise-linear... 相似文献
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Dany Spaggiari Laurent Geiser Youssef Daali Serge Rudaz 《Analytical and bioanalytical chemistry》2014,406(20):4875-4887
The cocktail approach is an advantageous strategy used to monitor the activities of several cytochromes P450 (CYPs) in a single test to increase the throughput of in vitro phenotyping studies. In this study, a cocktail mixture was developed with eight CYP-specific probe substrates to simultaneously evaluate the activity of the most important CYPs, namely, CYP1A2, CYP2A6, CYP2B6, CYP2C9, CYP2C19, CYP2D6, CYP2E1, and the CYP3A subfamily. After cocktail incubation in the presence of human liver microsomes (HLMs), the eight selected substrates and their specific metabolites were analyzed by ultra-high-pressure liquid chromatography and electrospray ionization quadrupole time-of-flight mass spectrometry. Qualitative and quantitative data were simultaneously acquired to produce an overview of the extended phase I biotransformation routes for each probe substrate in the HLMs and to generate phenotypic profiles of various HLMs. A comparison of the cocktail strategy with an individual substrate assay for each CYP produced similar results. Moreover, the cocktail was tested on HLMs with different allelic variants and/or in the presence of selective inhibitors. The results were in agreement with the genetic polymorphisms of the CYPs and the expected effect of the alterations. All of these experiments confirmed the reliability of this cocktail assay for phenotyping of the microsomal CYPs. 相似文献
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The present work is about the dynamic modelling and the experimental testing of magnetorheological (MR) dampers, especially at low frequency. The main improvement of this work over former models is the identification of dynamic parameters which are independent of the working conditions and vary only as a function of the current. A simple model is built on the basis of the literature and of a systematic experimental campaign, with the aim of simplifying the effort in retrieving the parameters and in controlling the system. The excitation current is introduced in the model as a variable, not only reducing the amount of test needed to assess the parameters, but also obtaining a faster model useful in motion control. A second order polynomial relationship between the applied current and the three variable parameters is found, showing a saturation effect at high currents. A verification test shows the reliability and the performance of the proposed model. 相似文献