6 resultados para ASYMMETRIC DIVISION

em Universidad de Alicante


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The BINAM-sulfonyl polymeric organocatalysts was prepared by the AIBN-promoted copolymerization of BINAM-derived sulfonamide, styrene and divinylbenzebe. The polymer catalyzed the asymmetric aldol reaction of aliphatic ketones with aromatic aldehydes to give the aldol products in up to 83% yield and with up to 95% ee. The catalysts could be recovered upt to 6 times with only a slight decrease on its activity.

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The dual activation of simple substrates by the combination of organocatalysis and palladium catalysis has been successfully applied in a variety of different asymmetric transformations. Thus, the asymmetric a-allylation of carbonyl compounds, a-fluorination of acyl derivatives, decarboxylative protonation of β-dicarbonyl compounds, cyclization reactions of alkynyl carbonyl compounds and β-functionalization of aldehydes have been efficiently achieved employing this double-catalytic methodology.

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Some chiral β-amino alcohols have been evaluated as potential ligands for the ruthenium-catalyzed asymmetric transfer hydrogenation (ATH) of N-phosphinyl ketimines in isopropyl alcohol. The ruthenium complex prepared from [RuCl2(p-cymene)]2 and (1S,2R)-1-amino-2-indanol has shown to be an efficient catalyst for the ATH of several N-(diphenylphosphinyl)imines, affording the reduction products in very good isolated yields and enantiomeric excesses up to 82%. The inherent rigidity of the indane ring system present in the ligand seems to be very important to achieve good enantioselectivities.

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Recoverable (Sa)-binam-l-prolinamide in combination with benzoic acid is used as catalysts in the direct aldol reaction between cycloalkyl, alkyl, and α-functionalized ketones and aldehydes under solvent-free reaction conditions. Three different methods are assayed: simple conventional magnetic stirring, magnetic stirring after previous dissolution in THF and evaporation, and ball mill technique. These procedures allow one to reduce not only the amount of required ketone to 2 equiv but also the reaction time to give the aldol products with regio-, diastereo-, and enantioselectivities comparable to those in organic or aqueous solvents. Generally anti-isomers are mainly obtained with enantioselectivities up to 97%. The reaction can be carried out under these conditions also using aldehydes as nucleophiles, yielding after in situ reduction of the aldol products the corresponding chiral 1,3-diols with moderate to high enantioselectivities mainly as anti-isomers. The aldol reaction has been studied by the use of positive ESI-MS technique, providing the evidence of the formation of the corresponding enamine−iminium intermediates.

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This paper considers the influence of business cycles and economic crises on tourism destinations competitiveness. This competitiveness is measured by its share in world tourism. Analysing a period of forty years, the differential permanent or temporary effects that economic crises has on competitiveness of mature and emerging destinations are observed. Furthermore, it identifies the economic transmission mechanisms operating within this context, analysing them using the framework of the most relevant explanatory models of tourism destination competitiveness. The preliminary results obtained suggest that the effects of these shocks on competitiveness are not neutral. In mature destinations the negative effects are more persistent in highly intensive crises. In emerging destinations with a growing natural trend on tourism demand, the effects of the economic crises are softer and limited, reinforcing the process of convergence between destinations. This effect works through two basic transmission mechanisms: the reduction of internal and external tourism demand and the decrease on investment.

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An asymmetric aqueous capacitor was constructed by employing zeolite-templated carbon (ZTC) as a pseudocapacitive positive electrode and KOH-activated carbon as a stable negative electrode. The asymmetric capacitor can be operated with the working voltage of 1.4 V, and exhibits an energy density that is comparable to those of conventional capacitors utilizing organic electrolytes, thanks to the large pseudocapacitance of ZTC. Despite relatively thick electrode (0.2 mm) configuration, the asymmetric capacitor could be well operated under a current density of 500 mA g −1.