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Philippe Zinck Andreia Valente Fanny Bonnet Ana Violante André Mortreux Marc Visseaux Simona Ilinca Rob Duchateau Pascal Roussel 《Journal of polymer science. Part A, Polymer chemistry》2010,48(4):802-814
The ability of various rare earth borohydride and chloride complexes/n‐butylethylmagnesium systems to operate styrene chain transfer polymerization in mild conditions has been assessed. Thirteen precatalysts have been considered: the rare earth trisborohydrides Ln(BH4)3(THF)x (x = 3, Ln = Nd (1), La (2), Sm (3), x = 2, Ln = Y (4), Sc (5)), the rare earth chlorides LnCl3(THF)x (x = 3, Ln = Nd (6), La (7), Sm (8), Y (9), x = 2, Ln = Sc (10)), the mixed La(BH4)2Cl(THF)2.6 (11) and the half‐lanthanidocenes Cp*Ln(BH4)2(THF)2 (Ln = Nd (12), La (13)). Six systems were found to be active precatalysts for the polymerization of styrene. 1 , 2 , and 11 led to an efficient transmetalation of the growing polystyrene chain with the simultaneous occurrence of βH elimination, whereas 7 , 12 , and 13 led to catalyzed chain growth behavior. It is noteworthy that the catalyzed chain growth obtained with 12 and 13 occurs with significant stereoselectivity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 802–814, 2010 相似文献
13.
Fotsop DF Roussi F Leverrier A Bretéché A Guéritte F 《The Journal of organic chemistry》2010,75(21):7412-7415
A short, convergent, and selective synthesis of meiogynin A, an inhibitor of the antiapoptotic protein Bcl-xL, has been performed. This synthesis, based on a biomimetic approach, allowed the determination of its absolute configuration. Three isomers of meiogynin A have also been elaborated. One of these was found to be three times more potent than the natural compound. 相似文献
14.
Highly trans‐Selective Arylation of Achmatowicz Rearrangement Products by Reductive γ‐Deoxygenation and Heck–Matsuda Reaction: Asymmetric Total Synthesis of (−)‐Musellarins A–C and Their Analogues 下载免费PDF全文
Zhilong Li Dr. Fanny C. F. Ip Prof. Dr. Nancy Y. Ip Prof. Dr. Rongbiao Tong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11152-11157
Fully functionalized pyranuloses derived from Achmatowicz rearrangement (AR) are versatile building blocks in organic synthesis. However, access to trans‐2,6‐dihydropyrans from pyranuloses remains underexplored. Herein, we report a new two‐step trans arylation of AR products to access 2,6‐trans‐dihydropyranones. This new trans‐arylation method built on numerous plausible, but unsuccessful, direct arylation reactions, including Ferrier‐type and Tsuji–Trost‐type reactions, was finally enabled by an unprecedented, highly regioselective γ‐deoxygenation of AR products by using Zn/HOAc and a diastereoselective Heck–Matsuda coupling. The synthetic utility of the reaction was demonstrated in the first asymmetric total synthesis of (?)‐musellarins A–C and 12 analogues in 11–12 steps. The brevity and efficiency of our synthetic route permitted preparation of enantiomerically pure musellarins and analogues (>20 mg) for preliminary cytotoxicity evaluation, which led us to identify two analogues with three‐to‐six times greater potency than the musellarins as promising new leads. 相似文献
15.
Hoffmann HC Assfour B Epperlein F Klein N Paasch S Senkovska I Kaskel S Seifert G Brunner E 《Journal of the American Chemical Society》2011,133(22):8681-8690
Recently, we have described the metal-organic framework Ni(2)(2,6-ndc)(2)(dabco), denoted as DUT-8(Ni) (1) (DUT = Dresden University of Technology, 2,6-ndc = 2,6-naphthalenedicarboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane). Upon adsorption of molecules such as nitrogen and xenon, this material exhibits a pronounced gate-pressure effect which is accompanied by a large change of the specific volume. Here, we describe the use of high-pressure in situ (129)Xe NMR spectroscopy, i.e., the NMR spectroscopic measurements of xenon adsorption/desorption isotherms and isobars, to characterize this effect. It appears that the pore system of DUT-8(Ni) takes up xenon until a liquid-like state is reached. Deeper insight into the interactions between the host DUT-8(Ni) and the guest atom xenon is gained from ab initio molecular dynamics (MD) simulations. van der Waals interactions are included for the first time in these calculations on a metal-organic framework compound. MD simulations allow the identification of preferred adsorption sites for xenon as well as insight into the breathing effect at a molecular scale. Grand canonical Monte Carlo (GCMC) simulations have been performed in order to simulate adsorption isotherms. Furthermore, the favorable influence of a sample pretreatment using solvent exchange and drying with supercritical CO(2) as well as the influence of repeated pore opening/closure processes, i.e., the "aging behavior" of the compound, can be visualized by (129)Xe NMR spectroscopy. 相似文献
16.
Dementin S Burlat B Fourmond V Leroux F Liebgott PP Abou Hamdan A Léger C Rousset M Guigliarelli B Bertrand P 《Journal of the American Chemical Society》2011,133(26):10211-10221
Electrons are transferred over long distances along chains of FeS clusters in hydrogenases, mitochondrial complexes, and many other respiratory enzymes. It is usually presumed that electron transfer is fast in these systems, despite the fact that there has been no direct measurement of rates of FeS-to-FeS electron transfer in any respiratory enzyme. In this context, we propose and apply to NiFe hydrogenase an original strategy that consists of quantitatively interpreting the variations of steady-state activity that result from changing the nature of the FeS clusters which connect the active site to the redox partner, and/or the nature of the redox partner. Rates of intra- and intermolecular electron transfer are deduced from such large data sets. The mutation-induced variations of electron transfer rates cannot be explained by changes in intercenter distances and reduction potentials. This establishes that FeS-to-FeS rate constants are extremely sensitive to the nature and coordination of the centers. 相似文献
17.
Hybrids of vinblastine and phomopsin, designed by a molecular modelling study, were elaborated in order to target tubulin. The key step of the synthesis (fragmentation and insertion of vindoline) was mediated by an internal N-carboxyanhydride (or O-acylcarbamate). This reaction was diastereospecific and addition of silver salts could reverse the diastereoselectivity. Even if the synthesized compounds are inactive, this synthesis represents an original example of a C-N fragmentation mediated by a N-carboxyanhydride. 相似文献
18.
A new carotenoid glycoside, namely neo-rehmannioside (1), together with five known compounds, 6-O-seco-hydroxyaeginetoyl ajugol (2), oxyrehmaionoside B (3), ajugol (4), geniposidic acid (5) and geniposide (6) was isolated from the 95% ethanol extract of dry roots of Rehmannia glutinosa. The structure of the new compound (1) was determined based on MS, IR, 1-D and 2-D NMR spectral data. 相似文献
19.
The lithium-oxygen battery with ether-based electrolytes 总被引:4,自引:0,他引:4
Freunberger SA Chen Y Drewett NE Hardwick LJ Bardé F Bruce PG 《Angewandte Chemie (International ed. in English)》2011,50(37):8609-8613
20.
Buffi N Merulla D Beutier J Barbaud F Beggah S van Lintel H Renaud P van der Meer JR 《Lab on a chip》2011,11(14):2369-2377
Contamination with arsenic is a recurring problem in both industrialized and developing countries. Drinking water supplies for large populations can have concentrations much higher than the permissible levels (for most European countries and the United States, 10 μg As per L; elsewhere, 50 μg As per L). Arsenic analysis requires high-end instruments, which are largely unavailable in developing countries. Bioassays based on genetically engineered bacteria have been proposed as suitable alternatives but such tests would profit from better standardization and direct incorporation into sensing devices. The goal of this work was to develop and test microfluidic devices in which bacterial bioreporters could be embedded, exposed and reporter signals detected, as a further step towards a complete miniaturized bacterial biosensor. The signal element in the biosensor is a nonpathogenic laboratory strain of Escherichia coli, which produces a variant of the green fluorescent protein after contact to arsenite and arsenate. E. coli bioreporter cells were encapsulated in agarose beads and incorporated into a microfluidic device where they were captured in 500 × 500 μm(2) cages and exposed to aqueous samples containing arsenic. Cell-beads frozen at -20 °C in the microfluidic chip retained inducibility for up to a month and arsenic samples with 10 or 50 μg L(-1) could be reproducibly discriminated from the blank. In the 0-50 μg L(-1) range and with an exposure time of 200 minutes, the rate of signal increase was linearly proportional to the arsenic concentration. The time needed to reliably and reproducibly detect a concentration of 50 μg L(-1) was 75-120 minutes, and 120-180 minutes for a concentration of 10 μg L(-1). 相似文献