Solvent-dependent enantioswitching in the Michael addition of α,α-disubstituted aldehydes to maleimides organocatalyzed by mono-N-Boc-protected cyclohexa-1,2-diamines

Enantiomerically pure mono-N-Boc-protected trans-cyclohexa-1,2-diamines are used as organocatalysts for the enantioselective conjugate addition of α,α-disubstituted aldehydes to maleimides. Using a single enantiomer of the organocatalyst, both enantiomeric forms of the resulting Michael adducts bearing a new quaternary stereocenter are obtained in high yields, by only changing the reaction solvent from chloroform (up to 86% ee) to aqueous DMF (up to 84% ee).We thank the financial support from the Spanish Ministerio de Economía y Competitividad (Project CTQ2011-24151), FEDER, the COST Action CM0905 ‘Organocatalysis’, and the University of Alicante

Enantioselective Solvent-Free Synthesis of 3-Alkyl-3-hydroxy-2-oxoindoles Catalyzed by Binam-Prolinamides

BINAM-prolinamides are very efficient catalyst for the synthesis of non-protected and N-benzyl isatin derivatives by using an aldol reaction between ketones and isatins under solvent-free conditions. The results in terms of diastereo- and enantioselectivities are good, up to 99% de and 97% ee, and higher to those previously reported in the literature under similar reaction conditions. A high variation of the results is observed depending on the structure of the isatin and the ketone used in the process. While 90% of ee and 97% ee, respectively, is obtained by using (Ra)-BINAM-l-(bis)prolinamide as catalyst in the addition of cyclohexanone and α-methoxyacetone to free isatin, 90% ee is achieved for the reaction between N-benzyl isatin and acetone using N-tosyl BINAM-l-prolinamide as catalyst. This reaction is also carried out using a silica BINAM-l-prolinamide supported catalyst under solvent-free conditions, which can be reused up to five times giving similar results.This work was financially supported by the Ministerio de Economia y Competitividad (MINECO: Projects: CTQ2010-20387 and Consolider INGENIO CSD2007-0006), FEDER, the Generalitat Valenciana (Prometeo/2009/039, the University of Alicante and the EU (ORCA action CM0905). A.B.-C. thanks the Spanish MICINN for a predoctoral fellowship (FPU AP2009-3601)

Enantioselective addition of aryl ketones and acetone to nitroalkenes organocatalyzed by carbamate-monoprotected cyclohexa-1,2-diamines

Enantiomerically pure carbamate-monoprotected trans-cyclohexane-1,2-diamines are used as chiral organocatalysts for the addition of aryl ketones and acetone to nitroalkenes to give enantioenriched β-substituted γ-nitroketones. The reaction was performed in the presence of 3,4-dimethoxybenzoic acid as an additive, in chloroform as the solvent at room temperature, achieving enantioselectivities up to 96%. Theoretical calculations are used to justify the observed sense of the stereoinduction.We thank the financial support from the Spanish Ministerio de Economía y Competitividad (project CTQ2011-24151), FEDER, the COST Action CM0905 ‘Organocatalysis’, the FP7 Marie Curie Action of the European Commission via the ITN ECHONET Network (FP7-MCITN-2012-316379), and the universities of Alicante and the Basque Country

Trivianometrics, una competición académica por equipos en el aula de Econometría Financiera.

Memoria en formato artículo de los resultados del proyecto de innovación docente PI_14_011 realizado en la Universidad de Cádiz durante el curso 2013/14. El proyecto recibió el tercer premio de innovación docente y diploma de excelencia otorgado por la Unidad de Innovación Docente de la UCA y el Consejo Social de la Universidad de Cádiz. http://www.uca.es/recursos/doc/Unidades/Unidad_Innovacion/Innovacion_Docente/2013_2014/1266175410_285201512844.pdfMotivar a los alumnos para estudiar con regularidad y participar en clase es una tarea compleja pero fundamental en asignaturas de aprendizaje continuo, donde los nuevos conocimientos se fundamentan en conocimientos previos adquiridos en las mismas. Con el objeto de incrementar el interés y estudio de la asignatura, propusimos a los alumnos participar en una competición académica por equipos donde se pone a prueba sus conocimientos de Econometría Financiera. El diseño de Trivianometrics combina dos elementos fundamentales en el aprendizaje: 1) trabajo continuo durante el curso y 2) un incentivo a corto plazo que motive a superar las dificultades de la materia de estudio. La competición se llevó a cabo durante el curso 2013/14 donde se creó una clasificación de equipos a partir de los puntos obtenidos en mini rondas de preguntas. Semanalmente, los alumnos tenían la posibilidad de ganar puntos para su equipo y mejorar la clasificación que se actualizaba al final de cada ronda. La distribución de los puntos se planificó de modo que se mantuviera el interés hasta el final. Tras desarrollarse la competición, se nombraron tres equipos ganadores que fueron recompensados con una nota extra en el examen y el reconocimiento público en clase con la entrega de un diploma de recuerdo. Al final del curso, los alumnos rellenaron un encuesta de opinión sobre la utilidad y los efectos del Trivianometrics en su motivación, proceso de aprendizaje y nota final de la asignatura con resultados muy satisfactorios. Más del 70% de los alumnos encuestados consideró que la actividad había tenido efectos positivos en su estudio regular. Además, nos sorprendió gratamente que más de la mitad de los alumnos consideró más motivador el reconocimiento hacia los ganadores que los puntos extra en el examen.Unidad de Innovación Docente UCA, Universidad de Cádi

El uso de códigos QR para mejorar en Econometría. Una experiencia docente.

Memoria final en formato artículo del proyecto de innovación docente PI_13_016. El proyecto fue llevado a cabo durante el curso académico 2012/13 y recibió un accésit y diploma con mención de excelencia por la Unidad de Innovación Docente y el Consejo Social de la Universidad de Cádiz. http://www.uca.es/recursos/doc/Unidades/Unidad_Innovacion/Innovacion_Docente/2012_2013/891466831_195201411523.pdfLos teléfonos móviles, máximos representantes de la integración tecnológica en nuestra sociedad, siguen ampliando su oferta de aplicaciones para facilitar nuestra vida diaria. Sin embargo, el mundo formativo continúa sin dar el paso definitivo a estos nuevos dispositivos. Con el trasfondo de que nuestros estudiantes empiecen a utilizar sus móviles en actividades formativas (m-learning) y con el objetivo de facilitar el aprendizaje de la asignatura de Econometría, se desarrolló una serie de actividades disponibles en el móvil mediante la lectura de códigos QR que permiten a los alumnos afianzar conceptos sobre la materia de estudio. Al finalizar el curso se realizó una encuesta de opinión cuyos resultados se analizaron para detectar los factores que influyen en el uso del móvil en las actividades que se pusieron a disposición de los estudiantes. Los principales resultados muestran la importancia de tener un conocimiento previo en la lectura de códigos QR para que los alumnos consideren esta actividad una ventaja en lugar de un inconveniente. Asimismo, se detectó que ventajas del móvil como la inmediatez de uso y la portabilidad pueden quedar menoscabadas por la lentitud de las conexiones de datos y el reducido tamaño de las pantallas de estos dispositivos.Unidad de Innovación Docente UCA, Universidad de CádizEl archivo contiene la memoria en formato artículo: 4 página

Pursuing Chemical Efficiency by Using Supported Organocatalysts for Asymmetric Reactions under Aqueous Conditions

Over the past decade, a great effort has been made by the chemical community to improve the efficiency of organic transformations and allow sustainable processes. Merging the use of supported and recyclable organocatalysts and aqueous conditions for the asymmetric synthesis of valuable molecules, has led to outstanding contributions in the area of green chemistry. Recent progresses in the field include the implementation of these methodologies in the large scale production of chiral molecules using automated flow chemistry.This work was financially supported by the University of Alicante (VIGROB-173, GRE12-03, UAUSTI13-01, UAUSTI13-02)

Asymmetric Conjugate Addition of α,α-Disubstituted Aldehydes to Nitroalkenes Organocatalyzed by Chiral Monosalicylamides from trans-Cyclohexane-1,2-Diamines

Primary amine-salicylamides derived from chiral trans-cyclohexane-1,2-diamines are used as organocatalysts for the enantioselective conjugate addition of α,α-disubstituted aldehydes to arylated and heteroarylated nitroalkenes. The reaction is performed in the presence of 4-dimethylaminopyridine as an additive in dichloromethane as a solvent at room temperature. The corresponding enantioenriched γ-nitroaldehydes are obtained with enantioselectivities up to 95%. Theoretical calculations are used to justify the reasons of the stereoinduction.We thank the financial support from the Spanish Ministerio de Economía, Industria y Competitividad (CTQ2015-66624-P) and the University of Alicante (VIGROB-173, UAUSTI17-06). J.F.-F. thanks the Vicerrectorado de Investigación y Transferencia del Conocimiento de la Universidad de Alicante for a fellowship. We also thank the Basque Government (GIC15/03, IT1033-16) for financial support, and the General Research Services (IZO/SGI SGIker) of the University of the Basque Country for human and technical support

Stereoselective synthesis of 1,3-disubstituted dihydroisoquinolines vial-phenylalanine-derived dihydroisoquinoline N-oxides.

The preparation of chiral pool-derived nitrone 3 and its use in the protecting-group free, stereoselective synthesis of a range of 1,3-disubstituted tetrahydroisoquinolines is described. Grignard reagent additions to nitrone 3 yielded trans-1,3-disubstituted N-hydroxytetrahydroisoquinolines 6 with good levels of selectivity, while 1,3-dipolar cycloadditions to this nitrone provided access to 3-(2-hydroxyalkyl)isoquinolines 12 as single diastereomers

Chiral Aminocarbamates Derived from trans-Cyclohexane-1,2-Diamines as Organocatalysts in Conjugate Addition Reactions

The thesis has been divided in two chapters: Chapter I describes the preparation of primary-amine monocarbamates from enantiopure trans-cyclohexane-1,2-diamines and their use as chiral organocatalysts in the enantioselective Michael addition reaction of aldehydes and ketones to maleimides, to synthesize enantiomerically enriched substituted succinimides. In the conjugate addition reaction of aldehydes to maleimides in conventional volatile organic solvents, it has been found that these organocatalysts are able to generate both enantiomers of the corresponding succinimide using only one enantiomeric form of the catalyst, just by changing the polarity of the solvent. Theoretical calculations justify the mechanism through which this inversion of enantioinduction occurred. In addition, these organocatalysts were used in the enantioselective Michael addition reaction of aldehydes to maleimides, using Deep Eutectic Solvents (DES) as recyclable and environmentally sustainable reaction medium, yielding the corresponding succinimides with excellent yields and high enantioselectivities (up to 94%). The succinimides can be extracted from the DES, which retains the chiral organocatalyst, allowing to reuse both solvent and catalyst. Moreover, the conjugate addition of ketones to maleimides using conventional solvents, allows obtaining the corresponding succinimides with excellent yields but with moderate enantioselectivities (up to 66%). Chapter II shows the results obtained in the enantioselective Michael addition reaction of aldehydes and ketones to nitroalkenes, using the former trans-cyclohexane-1,2-diamine-derived aminocarbamates as chiral organocatalysts, obtaining enantioenriched γ-nitrocarbonyl compounds. In the conjugate addition of isobutyraldehyde to nitroalkenes, the corresponding γ-nitroaldehydes were obtained with enantioselectivities up to 84%. In addition, the enantioselective conjugate addition reaction of ketones to nitroalkenes allowed to obtain interesting γ-nitroketones with high enantioselectivities (up to 96%). Theoretical calculations justify the mechanism involved during this enantioselective process

Chiral Aminocarbamates Derived from trans-Cyclohexane-1,2-Diamines as Organocatalysts in Conjugate Addition Reactions

The thesis has been divided in two chapters: Chapter I describes the preparation of primary-amine monocarbamates from enantiopure trans-cyclohexane-1,2-diamines and their use as chiral organocatalysts in the enantioselective Michael addition reaction of aldehydes and ketones to maleimides, to synthesize enantiomerically enriched substituted succinimides. In the conjugate addition reaction of aldehydes to maleimides in conventional volatile organic solvents, it has been found that these organocatalysts are able to generate both enantiomers of the corresponding succinimide using only one enantiomeric form of the catalyst, just by changing the polarity of the solvent. Theoretical calculations justify the mechanism through which this inversion of enantioinduction occurred. In addition, these organocatalysts were used in the enantioselective Michael addition reaction of aldehydes to maleimides, using Deep Eutectic Solvents (DES) as recyclable and environmentally sustainable reaction medium, yielding the corresponding succinimides with excellent yields and high enantioselectivities (up to 94%). The succinimides can be extracted from the DES, which retains the chiral organocatalyst, allowing to reuse both solvent and catalyst. Moreover, the conjugate addition of ketones to maleimides using conventional solvents, allows obtaining the corresponding succinimides with excellent yields but with moderate enantioselectivities (up to 66%). Chapter II shows the results obtained in the enantioselective Michael addition reaction of aldehydes and ketones to nitroalkenes, using the former trans-cyclohexane-1,2-diamine-derived aminocarbamates as chiral organocatalysts, obtaining enantioenriched γ-nitrocarbonyl compounds. In the conjugate addition of isobutyraldehyde to nitroalkenes, the corresponding γ-nitroaldehydes were obtained with enantioselectivities up to 84%. In addition, the enantioselective conjugate addition reaction of ketones to nitroalkenes allowed to obtain interesting γ-nitroketones with high enantioselectivities (up to 96%). Theoretical calculations justify the mechanism involved during this enantioselective process