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排序方式: 共有1215条查询结果,搜索用时 171 毫秒
1.
Na Shao Xueyang Liu Dr. Valérie Monnier Dr. Laurence Charles Dr. Jean Rodriguez Dr. Cyril Bressy Dr. Adrien Quintard 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(5):e202103874
Elaboration of enantioenriched complex acyclic stereotriads represents a challenge for modern synthesis even more when fluorinated tetrasubstituted stereocenters are targeted. We have been able to develop a simple strategy in a sequence of two unprecedented steps combining a diastereoselective aldol-Tishchenko reaction and an enantioselective organocatalyzed kinetic resolution. The aldol-Tishchenko reaction directly generates a large panel of acyclic 1,3-diols possessing a fluorinated tetrasubstituted stereocenter by condensation of fluorinated ketones with aldehydes under very mild basic conditions. The anti 1,3-diols featuring three contiguous stereogenic centers are generated with excellent diastereocontrol (typically >99 : 1 dr). Depending upon the precursors both diastereomers of stereotriads are accessible through this flexible reaction. Furthermore, from the obtained racemic scaffolds, development of an organocatalyzed kinetic resolution enabled to generate the desired enantioenriched stereotriads with excellent selectivity (typically er >95 : 5). 相似文献
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Tahya Bamine Edouard Boivin Christian Masquelier Laurence Croguennec Elodie Salager Dany Carlier 《Magnetic resonance in chemistry : MRC》2020,58(11):1109-1117
7Li, 31P, and 19F solid-state nuclear magnetic resonance (NMR) spectroscopy was used to investigate the local arrangement of oxygen and fluorine in LiVPO4F1-yOy materials, interesting as positive electrode materials for Li-ion batteries. From the evolution of the 1D spectra versus y, 2D 7Li radiofrequency-driven recoupling (RFDR) experiments combined, and a tentative signal assignment based on density functional theory (DFT) calculations, it appears that F and O are not randomly dispersed on the bridging X position between two X–VO4–X octahedra (X = O or F) but tend to segregate at a local scale. Using DFT calculations, we analyzed the impact of the different local environments on the local electronic structure. Depending on the nature of the VO4X2 environments, vanadium ions are either in the +III or in the +IV oxidation state and can exhibit different distributions of their unpaired electron(s) on the d orbitals. Based on those different local electronic structures and on the computed Fermi contact shifts, we discuss the impact on the spin transfer mechanism on adjacent nuclei and propose tentative signal assignments. The O/F clustering tendency is discussed in relation with the formation of short VIVO vanadyl bonds with a very specific electronic structure and possible cooperative effect along the chain. 相似文献
4.
Carassus Laurence Rásonyi Miklós 《Journal of Optimization Theory and Applications》2020,186(1):248-263
Journal of Optimization Theory and Applications - We consider infinite-dimensional optimization problems motivated by the financial model called Arbitrage Pricing Theory. Using probabilistic and... 相似文献
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Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)2(μ,η6:η6‐P6)] Towards the “Naked” Cations Cu+, Ag+, and Tl+ 下载免费PDF全文
Martin Fleischmann Fabian Dielmann Laurence J. Gregoriades Eugenia V. Peresypkina Alexander V. Virovets Sebastian Huber Alexey Y. Timoshkin Gbor Balzs Manfred Scheer 《Angewandte Chemie (International ed. in English)》2015,54(44):13110-13115
Although the cyclo‐P6 complex [(Cp*Mo)2(μ,η6:η6‐P6)] ( 1 ) was reported 30 years ago, little is known about its chemistry. Herein, we report a high‐yielding synthesis of 1 , the complex 2 , which contains an unprecedented cyclo‐P10 ligand, and the reactivity of 1 towards the “naked” cations Cu+, Ag+, and Tl+. Besides the formation of the single oxidation products 3 a,b which have a bisallylic distorted cyclo‐P6 middle deck, the [M( 1 )2]+ complexes are described which show distorted square‐planar (M=Cu( 4 a ), Ag( 4 b )) or distorted tetrahedral coordinated (M=Cu( 5 )) M+ cations. The choice of solvent enabled control over the reaction outcome for Cu+, as proved by powder XRD and supported by DFT calculations. The reaction with Tl+ affords a layered two‐dimensional coordination network in the solid state. 相似文献
6.
Automated solvent system screening for the preparative countercurrent chromatography of pharmaceutical discovery compounds 下载免费PDF全文
James Bradow Frank Riley Laurence Philippe Qi Yan Brandon Schuff Guy H. Harris 《Journal of separation science》2015,38(23):3983-3991
A fully automated countercurrent chromatography system has been constructed to rapidly screen the commonly used heptane/ethyl acetate/methanol/water solvent system series and translate the results to preparative scale separations. The system utilizes “on‐demand” preparation of the heptane/ethyl acetate/methanol/water solvent system upper and lower phases. Elution‐extrusion countercurrent chromatography was combined with non‐dynamic equilibrium injection reducing the screening time for each heptane/ethyl acetate/methanol/water system to 17 min. The result enabled solvent system development to be reduced to under 2 h. The countercurrent chromatography system was interfaced with a mass spectrometer to allow selective detection of target components in crude medicinal chemistry reaction mixtures. Mass‐directed preparative countercurrent chromatography purification was demonstrated for the first time using a synthetic tetrazole epoxide derived from a routine medicinal chemistry support workflow. 相似文献
7.
Frank W. Lewis Laurence M. Harwood Michael J. Hudson Andreas Geist Valery N. Kozhevnikov Petr Distler Jan John 《Chemical science》2015,6(8):4812-4821
We report the first examples of hydrophilic 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) ligands, and their applications as actinide(iii) selective aqueous complexing agents. The combination of a hydrophobic diamide ligand in the organic phase and a hydrophilic tetrasulfonated bis-triazine ligand in the aqueous phase is able to separate Am(iii) from Eu(iii) by selective Am(iii) complex formation across a range of nitric acid concentrations with very high selectivities, and without the use of buffers. In contrast, disulfonated bis-triazine ligands are unable to separate Am(iii) from Eu(iii) in this system. The greater ability of the tetrasulfonated ligands to retain Am(iii) selectively in the aqueous phase than the corresponding disulfonated ligands appears to be due to the higher aqueous solubilities of the complexes of the tetrasulfonated ligands with Am(iii). The selectivities for Am(iii) complexation observed with hydrophilic tetrasulfonated bis-triazine ligands are in many cases far higher than those found with the polyaminocarboxylate ligands previously used as actinide-selective complexing agents, and are comparable to those found with the parent hydrophobic bis-triazine ligands. Thus we demonstrate a feasible alternative method to separate actinides from lanthanides than the widely studied approach of selective actinide extraction with hydrophobic bis-1,2,4-triazine ligands such as CyMe4-BTBP and CyMe4-BTPhen. 相似文献
8.
Mathematical Programming - Switching machines on and off is an important aspect of unit commitment problems and production planning problems, among others. Here we study tight mixed integer... 相似文献
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10.
Franck Charmantray Nadia Touisni Laurence Hecquet Thierry Noguer Christine Mousty 《Electroanalysis》2015,27(6):1341-1344
This paper describes the development of an amperometric biosensor based on galactose oxidase (GAOx) immobilization within a laponite clay film deposited on Carbon Screen‐Printed Electrodes modified by electrodeposited Prussian Blue and coated with poly‐(O‐phenylenediamine) (PPD/PB/CSPEs). Amperometric performances of GAOx@laponite/PPD/PB/CSPEs bioelectrodes were determined using several GAOx substrates. Using these modified electrodes the reduction of enzymatically generated hydrogen peroxide was performed at ?0.2 V vs. Ag‐AgCl. In an initial attempt, E.Coli transketolase activity on its immobilized form was followed using a bienzymatic GAOx‐TK biosensor. 相似文献