Hydrazone Activation in the Aminocatalytic Cascade Reaction for the Synthesis of Tetrahydroindolizines.

In this Letter, we demonstrate the usefulness of hydrazone activation for the synthesis of biologically relevant tetrahydroindolizines. A pyrrol-derived hydrazone bearing a Michael acceptor moiety in the -alkyl side chain has been designed with the aim of participating in the aminocatalytic cascade reaction leading to the annulation of the new six-membered heterocyclic scaffold. The application of ()-(-)-α,α-diphenyl-2-pyrrolidinemethanol trimethylsilyl ether as the aminocatalyst allows for the iminium ion-enamine-mediated cascade to proceed in a fully stereoselective manner.

Asymmetric Organocatalysis in the Remote (3 + 2)-Cycloaddition to 4-(Alk-1-en-1-yl)-3-cyanocoumarins.

The application of organocatalytic bifunctional activation in the remote (3 + 2)-cycloaddition between 4-(alk-1-en-1-yl)-3-cyanocoumarins and imines derived from salicylaldehyde is demonstrated. Products, bearing two biologically relevant units, have been obtained with good chemical and stereochemical efficiency. The stereochemical outcome of the process results from the application of a quinine-derived catalyst.

Vinylogous hydrazone strategy for the organocatalytic alkylation of heteroaromatic derivatives.

A new umpolung approach for the asymmetric Friedel-Crafts-type alkylation of electron-poor heteroaromatic systems has been developed. It is based on the vinylogous reactivity of hydrazones derived from heteroaromatic aldehydes. The donating effect of the hydrazone moiety can be efficiently transferred over the heteroaromatic system activating it towards an asymmetric Friedel-Crafts reaction with α,β-unsaturated aldehydes realized under aminocatalytic conditions.

A novel route to a chiral building block for the preparation of cyclopentenyl carbocyclic nucleosides. Synthesis and anticancer activity of enantiomeric neplanocins A.

The synthesis of both enantiomers of 3-[(-butyldimethylsilyl)oxy]methyl-4,5--isopropylidenecyclopent-2-en-1-ol was accomplished in six steps based on optically inactive dimethyl -tartrate. This key intermediate in the synthesis of cyclopentenyl carbocyclic nucleosides was subsequently applied in the preparation of enantiomeric neplanocins A. The toxic effect of these compounds was investigated for a series of suspension and adherent cancer cell lines and normal human fibroblasts.

Highly Fluorescent Distyrylnaphthalene Derivatives as a Tool for Visualization of Cellular Membranes.

Fluorescent imaging, which is an important interdisciplinary field bridging research from organic chemistry, biochemistry and cell biology has been applied for multi-dimensional detection, visualization and characterization of biological structures and processes. Especially valuable is the possibility to monitor cellular processes in real time using fluorescent probes. In this work, conjugated oligoelectrolytes and neutral derivatives with the distyrylnaphthalene core (SN-COEs) were designed, synthetized and tested for biological properties as membrane-specific fluorescent dyes for the visualization of membrane-dependent cellular processes.

Theoretical and experimental study on the effects of pH and surfactant on the internal charge transfer process in distyrylnaphthalene-based conjugated oligoelectrolytes.

In this study we have investigated the effects of pH and surfactant on the internal charge transfer (ICT) process in the DSNN derivative, DSNN-NMe (4,4'-bis(4'-(N,N-bis(6″-(N,N,N-trimethylammonium)hexyl)amino)-styryl) naphthalene tetraiodide) with the aim to show that environmentally-induced changes in the degree of ICT process determine the spectral response of the DSNN chromophore. Obtained results showed that DSNN chromophore exhibits evident changes in linear optical properties (absorption/emission wavelengths, quantum yield) upon protonation. These changes are a manifestation of the attenuation of the internal charge transfer processes, which accompanies binding of proton to the nitrogen atoms of the dialkylamino groups at the termini of DSNN chromophore.

Fluorescence and confocal imaging of mammalian cells using conjugated oligoelectrolytes with phenylenevinylene core.

Over the last few years, considerable efforts are taken, in order to find a molecular fluorescent probe fulfilling their applicability requirements. Due to a good optical properties and affinity to biological structures conjugated oligoelectrolytes (COEs) can be considered as a promising dyes for application in fluorescence-based bioimaging. In this work, we synthetized COEs with phenylenevinylene core (PV-COEs) and applied as fluorescent membranous-specific probes.

Synthesis of Enantiomerically Pure Stereomers of Rosaprostol.

Enantiopure stereomers of rosaprostol 1, an antiulcer drug, were synthesized from diastereomeric building blocks (-)-5a and (+)-5b. Conversion of (-)-5a into rosaprostol stereomer (-)-(1S,2R,5R)-1a was accomplished in nine steps in 18% overall yield. In this sequence, fully diastereoselective hydrogeneration of the endocyclic carbon double bond in the cyclopentenone ring was key, generating a new stereogenic center (C-2 in 1a).