Search results for "Selectivity"

Understanding the regioselectivity in hetero Diels–Alder reactions. An ELF analysis of the reaction between nitrosoethylene and 1-vinylpyrrolidine

2013

[EN] The regioselectivity in the hetero Diels-Alder reaction between nitrosoethylene 1 and 1-vinylpyrrolidine 2 has been studied by a comparative ELF bonding analysis along the IRC of the endo/ortho and endo/meta regioisomeric channels at the B3LYP/6-31G*. level. Along the most favorable endo/ortho regioisomeric channel, the C-C sigma bond is first formed by coupling of two pseudoradical centers located at the most electrophilic carbon of 1 and the most nucleophilic center of 2. Formation of these relevant pseudoradical centers, which depend on the total charge transfer process along the polar reaction, and not on the approach mode of each reagent, is well characterized by analysis of the a…

Chapter 9 The electrophilicity index in organic chemistry

2007

Abstract We review in this chapter the applications of theoretical scales of global and local electrophilicity to rationalize the reactivity and selectivity for a significant number of reactions in organic chemistry. The model is based on the global electrophilicity index, formerly introduced by Maynard et al. and further formalized by Parr et al. The global electrophilicity index categorizes, within a unique absolute scale, the propensity of electron acceptors to acquire additional electronic charge from the environment. The local extension of this index provides useful information about the active sites of electrophiles, thereby allowing the characterization of the intramolecular selectiv…

Selectivity tuning in pressurized-flow electrochromatography

1996

Abstract Pressurized-flow electrochromatography (PEC) is a developing separation technique in which both a pressure gradient and an electric field are applied across a packed capillary. In this work we present new results illustrating the principles and the potential of PEC. Home-made capillary columns with silica-based reversed phase packings were operated under PEC conditions separating low molecular weight analytes. Compared to the purely pressure-driven system enhanced selectivity for the charged analytes was observed. It is shown that the retention time of a retained cationic analyte in PEC can be calculated using the chromatographic capacity factor and the electrophoretic mobility of …

Enantioselective synthesis and absolute configurations of aculeatins A, B, D, and 6-epi-aculeatin D

2006

The three naturally occurring, bioactive spiroacetals aculeatins A, B, and D, as well as the non-natural 6-epi-aculeatin D have been synthesized for the first time in enantiopure form using an asymmetric allylation as the only chirality source. A further key step was a stereoselective aldol reaction with remote induction. The absolute configurations of the natural products have been established and an erroneous structural assignment has been corrected.

Narrowband digital filtering with random frequency hopping spread spectrum

2014

International audience; In digital signal filtering, channels with narrow bandwidth need high order digital filter to be selected without introducing modulation errors. If a carrier randomly switches from a channel to another as in military applications, or some civilian communication standards, it is necessary to detect and estimate these jumps before transposing and analyzing signals in the baseband. This paper presents a real time solution to filter narrow band signals with random frequency hopping spread spectrum. The proposed method is based on three steps. Firstly, the detection of Signal Frequency Hopping (SFH) using the Fast Fourier Transform (FFT), an algorithm to estimate the Domi…

2014

Abstract The enantiomeric and diastereomeric profiling of chiral pharmaceuticals (ephedrine, norephedrine, atenolol and venlafaxine) and illicit drugs (amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxy- N -methylamphetamine (MDMA) and 3,4-methylenedioxy- N -ethylamphetamine (MDEA)) was undertaken over a period of fourteen consecutive days in three wastewater treatment plants (WWTPs) in the city of Valencia, Spain. Degradation efficiency of WWTPs was found to be compound and enantiomer dependent. Selective enantiomer enrichment was observed for several target analytes. Amphetamine and MDMA were enriched with R (−)-enantiomers. 1 S ,2 S (+)-pseudoephedrine …

Trimeprazine is enantioselectively degraded by an activated sludge in ready biodegradability test conditions

2018

[EN] A great number of available pharmaceuticals are chiral compounds. Although they are usually manufactured as racemic mixtures, they can be enantioselectively biodegraded as a result of microbial processes. In this paper, a biodegradability assay in similar conditions to those recommended in OECD tests of enantiomers of trimeprazine (a phenothiazine employed as a racemate) is carried out. Experiments were performed in batch mode using a minimal salts medium inoculated with an activated sludge (collected from a Valencian Waste Water Treatment Plant, WWTP) and supplemented with the racemate. The concentration of the enantiomers of trimeprazine were monitored by means of a chiral HPLC metho…

Design, characterization and comparison of materials based on β and γ cyclodextrin covalently connected to microporous silica for environmental analy…

2018

Abstract Determination of organic pollutants in environmental samples presents great difficulties due to the lack of sensitivity and selectivity in many of the existing analytical methods. In this work, the efficiency of materials based on silica structures containing bounded γ-cyclodextrin has been evaluated to determinate phenolic compounds and polycyclic aromatic hydrocarbons in air and water samples, respectively, in comparison with materials made of β-cyclodextrin. According to the results obtained for the material characterization, the new γ-cyclodextrin solid phase does not apparently present any porosity when used in air samples, but it has been shown to work efficiently for the pre…

Gold(I) Complexes Nuclearity in Constrained Ferrocenyl Diphosphines: Dramatic Effect in Gold‐Catalyzed Enyne Cycloisomerization

2020

International audience; Di-tert-butylated-bis(phosphino)ferrocene ligands bearing phosphino substituents R (R=phenyl, cyclohexyl, isopropyl, mesityl, or furyl) allow tuning the selective formation of Au(I) halide complexes. Thus, dinuclear linear twocoordinate, but also rare mononuclear trigonal three-coordinate and tetrahedral four-coordinate complexes were formed upon tuning of the conditions. Both Au(I) chloride and rarer Au(I) iodide complexes were synthesized, and their X-ray diffraction analysis are reported. The significance of the control of structure and nuclearity in Au(I) complexes is further illustrated herein by its strong effect on the efficiency and selectivity of gold-cataly…

A combined experimental and theoretical study of the thermal [3+2] cycloaddition of carbonyl ylides with activated alkenes

2018

International audience; 4-Benzoyl-3,5-diaryltetrahydrofuran-2,2-dicarbonitriles were first synthesized from 2,2-dicyano-3-aryloxiranes and chalcones at toluene reflux; the 4,5-cis products proved to be predominantly formed and were isolated. Whereas shortened reaction times were observed by using microwave irradiation or catalytic cuprous chloride, no significant stereoselectivity change was in general noticed. Reacting 2,2-dicyano-3-aryloxiranes with 2-cyclopentenone next afforded 3-aryl-4-oxohexahydro-1H-cyclopenta[c]furan-1,1-dicarbonitriles, and the endo stereoisomers were isolated. That no stereoselectivity change was noticed in the presence of cuprous chloride rather suggests an impac…