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.

Experimentació en síntesi química: química inorgànica

Aquest llibre de laboratori de química inorgànica està dirigit a alumnes que s'introdueixen per primera vegada en l'experimentació de síntesi inorgànica. Per aquest motiu, es pretén no sols que l'alumne adquiresca coneixements de química inorgànica sinó que els integre dins la metodologia de treball de la química inorgànica (els coneixements essencials de la qual són la teoria i l'experimentació).

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).

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.

Solvent-Induced Reversal of Enantioselectivity in the Synthesis of Succinimides by the Addition of Aldehydes to Maleimides Catalysed by Carbamate-Monoprotected 1,2-Diamines

A simple change in the polarity of the solvent allows both enantiomers of substituted succinimides to be obtained in the enantioselective conjugate addition reaction of aldehydes, mainly α,α-disubstituted, to maleimides catalysed by chiral carbamate-monoprotected trans-cyclohexane-1,2-diamines. Using a single enantiomer of the organocatalyst, both enantiomers of the resulting Michael adducts are obtained in high yields by simply changing the reaction solvent from aqueous DMF (up to 84 % ee) to chloroform (up to 86 % ee). Theoretical calculations are used to explain this uncommon reversal of the enantioselectivity; two transition state orientations of different polarities are differently favoured in polar or nonpolar solvents.

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.

Ciències socials i la seua didàctica

Aquest quadern ha sorgit amb l'objectiu de facilitar el material didàctic necessari per al seguiment de l'assignatura de Ciències socials i la seua didàctica, ubicada en el segon curs de Magisteri, especialitat Educació Primària. Els alumnes d'aquesta titulació tenen un pla d'estudi molt dens, i una simple observació posa de manifest la falta de temps per atendre la seua formació. Al mateix temps els avanços tant en la didàctica com en les ciències de referència, difosos en revistes especialitzades, llibres de congressos, o temàtics, ens aconsellen realitzar una selecció i presentar una síntesi, que servesca de punt de partida per tot l'alumnat que tinga una mínima inquietud. Per aquesta raó dins dels primers capítols i activitats d'aula es presenten les principals fonts d'informació com bibliografia, hemeroteca o direccions d'Internet. La Universitat d'Alacant, conscient que molts alumnes volen estudiar en valencià, ofereix al professors, a través del Secretariat de Promoció del Valencià, l'oportunitat d'elaborar materials docents en aquesta llengua. Per tant l'objectiu d'aquest quadern també és atendre la demanda social existent i proporcionar el material didàctic bàsic pel seguiment de l'assignatura de Ciències socials i la seua didàctica. Els continguts seleccionats per al quadern estan definits pel descriptor que marca la normativa i els principis de la ciència, que el docent a presentat als seus alumnes i que han sigut avaluats a classe al llarg de cinc cursos.

Modelatge basat en funcions per la aproximació als fenòmens naturals

Aquesta presentació resumeix les tècniques computacionals existents que aborden l'estudi dels fenòmens naturals i prososa una aproximació basada en funcions.

Catalytic asymmetric transfer hydrogenation of ketones: recent advances

In this review, we consider the main processes for the asymmetric transfer hydrogenation of ketones from 2008 up today. The most effective organometallic compounds (derived from Ru, Rh, Ir, Fe, Os, Ni, Co, and Re) and chiral ligands (derived from amino alcohols, diamines, sulfur- and phosphorus-containing compounds, as well as heterocyclic systems) will be shown paying special attention to functionalized substrates, tandem reactions, processes under non-conventional conditions, supported catalysts, dynamic kinetic resolutions, the use of water as a green solvent, theoretical and experimental studies on reaction mechanisms, enzymatic processes, and finally applications to the total synthesis of biologically active organic molecules.