Inmovilización de complejos organometálicos en soportes sólidos para aplicación en catálisis

La memoria de tesis titulada “Inmovilización de complejos organometálicos en soportes sólidos para aplicación en catálisis” presenta una serie de trabajos encaminados a la obtención de catalizadores híbridos, que sean estables, activos, selectivos y reutilizables en reacciones de hidrogenación e hidroformilación de olefinas. Para ello, se han estudiado diversos métodos para inmovilizar complejos metálicos en materiales carbonosos y sólidos inorgánicos: adsorción física, anclaje por formación de un enlace covalente e intercambio iónico. Estos catalizadores se han usado en las reacciones mencionadas, analizando sus propiedades catalíticas (actividad y selectividad), así como la robustez de los mismos y las posibilidades de reutilización.

Diseño de reactores heterogéneos. Tema 2. Reactores catalíticos

Reacción catalítica. Difusión. Reacción Heterogénea.

Coordinación y seguimiento de los tres primeros cursos del Grado en Ing. Sonido e Imagen en Telecomunicación

El reto de implantar los nuevos grados exige un continuado esfuerzo de coordinación de las asignaturas de cada curso y de los diferentes cursos entres sí. En este trabajo se presentan los resultados de los diferentes proyectos que se han realizado para coordinar las asignaturas de los tres primeros cursos del Grado en Ingeniería en Sonido e Imagen en Telecomunicación de la Escuela Politécnica Superior. Además se analiza la coordinación de los proyectos entre sí, analizando los cambios surgidos en las fichas de las asignaturas, evaluación, metodología, etc. También se presenta una puesta en común con los coordinadores de todos los cursos para realizar las recomendaciones de matriculación a los estudiantes que realizan su matrícula a tiempo parcial o no superan cada curso todos los créditos matriculados. Y por último, se estudia la continuidad con los contenidos de las asignaturas que comienzan su implantación en el siguiente curso y por otro lado la coordinación en la evaluación para eliminar las numerosas coincidencias de evaluaciones continuas, de diferentes actividades en cada semana.

Palladium and organocatalysis: an excellent recipe for asymmetric synthesis

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.

Chiral β-amino alcohols as ligands for the ruthenium-catalyzed asymmetric transfer hydrogenation of N-phosphinyl ketimines

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.

Enantioselective alkylation of β-keto esters promoted by dimeric Cinchona-derived ammonium salts as recoverable organocatalysts

Dimeric anthracenyldimethyl-derived Cinchona ammonium salts are used as chiral organocatalysts in 5 mol% for the phase-transfer enantioselective alkylation reaction of 2-alkoxycarbonyl-1-indanones with activated bromides. The corresponding adducts bearing a new all-carbon quaternary center are obtained usually in high yield and with moderate and opposite enantioselectivity (up to 55%) when using ammonium salts derived from quinidine and its pseudoenantiomer quinine as organocatalysts. These catalysts can be almost quantitatively recovered by precipitation in ether and reused.

A Highly Efficient Solvent-Free Asymmetric Direct Aldol Reaction Organocatalyzed by Recoverable (s)-Binam-L-Prolinamides. ESI-MS Evidence of the Enamine-Iminium Formation

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.

eFisioTrack: a telerehabilitation environment based on motion recognition using accelerometry

The growing demand for physical rehabilitation processes can result in the rising of costs and waiting lists, becoming a threat to healthcare services’ sustainability. Telerehabilitation solutions can help in this issue by discharging patients from points of care while improving their adherence to treatment. Sensing devices are used to collect data so that the physiotherapists can monitor and evaluate the patients’ activity in the scheduled sessions. This paper presents a software platform that aims to meet the needs of the rehabilitation experts and the patients along a physical rehabilitation plan, allowing its use in outpatient scenarios. It is meant to be low-cost and easy-to-use, improving patients and experts experience. We show the satisfactory results already obtained from its use, in terms of the accuracy evaluating the exercises, and the degree of users’ acceptance. We conclude that this platform is suitable and technically feasible to carry out rehabilitation plans outside the point of care.

Growing Neural Gas approach for obtaining homogeneous maps by restricting the insertion of new nodes

The Growing Neural Gas model is used widely in artificial neural networks. However, its application is limited in some contexts by the proliferation of nodes in dense areas of the input space. In this study, we introduce some modifications to address this problem by imposing three restrictions on the insertion of new nodes. Each restriction aims to maintain the homogeneous values of selected criteria. One criterion is related to the square error of classification and an alternative approach is proposed for avoiding additional computational costs. Three parameters are added that allow the regulation of the restriction criteria. The resulting algorithm allows models to be obtained that suit specific needs by specifying meaningful parameters.

Aqueous organocatalyzed aldol reaction of glyoxylic acid for the enantioselective synthesis of α-hydroxy-γ-keto acids

N-Tosyl-(Sa)-binam-L-prolinamide is an efficient catalyst for the aqueous aldol reaction, between glyoxylic acid, as monohydrate or aqueous solution, and ketones. This reaction led to the formation of chiral α-hydroxy-γ-keto carboxylic acids in high levels of diastereo- and enantioselectivities achieving mainly anti aldol products.

Adición conjugada de compuestos 1,3-dicarbonílicos a maleimidas catalizada por 2-aminobencimidazoles quirales

En la presente memoria se describe la síntesis y aplicación de diversos organocatalizadores quirates derivados de 2-aminobencimidazol en reacciones de adición Michael de compuestos 1,3-discarbonílicos a maleimidas. En este trabajo se ha preparado un organocatalizador quiral y reciclable con simetría C₂ derivado de bencimidazol y (1R,2R)-ciclohexano-1,2-diamina y se ha utilizado con éxito en la adición conjugada de β-dicetonas, β-cetoésteres y malonatos de dialquilo a maleimida y maleimidas N-sustituidas. La adición, que se lleva cabo en tolueno y a temperatura ambiente, conduce a las correspondientes succinimidas quirales con buenos rendimientos, moderadas diastereoselectividades y excelentes excesos enantioméricos. También se han realizado estudios mecanísticos mediante cálculos computacionales DFT y estudios de difusión por resonancia magnética nuclear para determinar el modo de actuación del catalizador y el estado de transición de la reacción de adición conjugada de compuestos 1,3-dicarbonílicos a maleimidas que han confirmado el estado de transición y mecanismo propuestos.

Enantioselective Michael addition of isobutyraldehyde to nitroalkenes organocatalyzed by chiral primary amine-guanidines

Primary amine-guanidines derived from trans-cyclohexane-1,2-diamines are used as organocatalysts for the enantioselective conjugate addition of isobutyraldehyde to arylated and heteroarylated nitroalkenes. The reaction was performed in the presence of imidazole as the additive in aqueous DMF as the solvent at 0 °C. The corresponding Michael adducts bearing a new stereocenter were obtained in high yields and with enantioselectivities of up to 80%. Theoretical calculations are used to justify the observed sense of the stereoinduction.

Enantioselective Michael addition of aldehydes to maleimides organocatalysed by chiral 1,2-diamines: an experimental and theoretical study

Simple and commercially available chiral 1,2-diamines were used as organocatalysts for the enantioselective conjugate addition of aldehydes, including α,α-disubstituted, to maleimides. The reaction was carried out in the presence of hexanedioic acid as an additive in aqueous solvents at room temperature. By employing (1S,2S)- and (1R,2R)-cyclohexane-1,2-diamine as organocatalysts, the corresponding Michael adducts bearing new stereocenters were obtained in high or quantitative yields with enantioselectivities of up to 92%, whereas the use of (1S,2S)-1,2-diphenylethane-1,2-diamine gave a much lower ee. Theoretical calculations were used to justify the observed sense of the stereoinduction.

Polymer-supported l-prolinol-based catalysts for the enantioselective addition of dialkylzinc reagents to N-(diphenylphosphinyl)imines

l-Prolinol-based ligands anchored to Merrifield or Wang-type resins have been shown to form efficient catalysts for the enantioselective addition of dialkylzinc reagents to N-(diphenylphosphinyl)imines. The enantioselectivity achieved with the polymeric catalyst (ee up to 88%) is slightly lower than the one obtained with the homogeneous ligand N-benzyl-l-prolinol, but the polymer-supported ligand presents the advantage of its recyclability: it can be recovered and used in up to six consecutive catalytic cycles with only a slight decrease in the enantiomeric excess. The phosphinamides obtained as addition products can be transformed into the corresponding enantiomerically enriched α-branched primary amines under mild acidic conditions.