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Phosphinite thioglycosmes, preparation method and use thereof as novel ligands in asymmetric catalysis.

Authors: Khiar, Noureddine; Suárez Jiménez, Belén; Fernández, I.;

Phosphinite thioglycosmes, preparation method and use thereof as novel ligands in asymmetric catalysis.

Abstract

[ES]Se describe un nuevo proceso sintético para la preparación de ligandos bidentados azufre/fósforo (S/P) a partir de carbohidratos. Los nuevos compuestos obtenidos son derivados de tioglicósidos, con un átomo de azufre en posición anomérica y por lo tanto son de tipo tioacetálico y no de tipo tioéter. Se describen igualmente procesos catalíticos y composición de catalizadores para alquilación y aminación alílicas, así como para la hidrogenación asimétrica. En todos los procesos catalíticos desarrollados se puede obtener selectivamente un isómero u otro utilizando en todos los casos azúcares de la serie D. Los procesos utilizan catalizadores en cuya composición hay un átomo de paladio o de radio y un fosfinito tioglicósido, donde la estructura del carbohidrato determina si la configuración del nuevo centro quiral creado será S o R.

[EN]A novel synthesis process for preparing sulphur/phosphorus (S/P) bidentate ligands from carbohydrates is described. The resulting novel compounds are thioglycoside derivatives with one anomerically positioned sulphur atom, meaning that they are thioacetals not thioethers. Catalytic processes and a catalyst composition for allyl amination and alkylation, as well as for asymmetric hydrogenation, are also described. One or another isomer can be obtained in all of the catalytic processes using D-series sugars in all cases. The processes use catalysts with a composition including a palladium or rhodium atom and a phosphinite thioglycoside, wherein the structure of the carbohydrate determines whether the resulting chiral centre will have an S configuration or an R configuration.

Fecha de Presentación internacional: 06.04.2006.- Titulares:Consejo Superior de Investigaciones Científicas (CSIC).- Universidad de Sevilla.

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