Engineering amphiphilic alkenyl lipids for self-assembly in functional hybrid nanostructures.

The development of biocompatible hybrid nanosystems for advanced functional applications presents significant challenges to the research community. Key obstacles include the poor solubility of these nanosystems in water and the difficulty of precisely controlling their nanostructure dimensions and composition. A promising approach to overcoming these challenges is the self-assembly of surfactant-based building blocks into well-ordered hybrid nanostructures.

Stereoselective Synthesis of Chiral -Symmetric 1,3- and 1,5-Bis-Sulfoxides Guided by the Horeau Principle: Understanding the Influence of the Carbon Chain Nature in Its Ability for Metal Coordination.

The stereoselective synthesis of two distinct types of -symmetric chiral bis-sulfoxides, 1,3- and 1,5-bis(sulfinyl) derivatives, has been achieved based on the DAG methodology. The 1,5-bis(sulfinyl) derivatives constitute a new family of tridentate chiral ligands thanks to the presence of an additional sulfenyl or sulfinyl group in the carbon chain acting as a bridge. A systematic development and optimization of two synthetic routes, one for each ligand family, have been undertaken, highlighting the strategic utilization of Horeau's law to enhance enantioselectivity.

Biological evaluation of carbohydrate-based aprepitant analogs for neuroblastoma treatment.

Different studies using Aprepitant, a NK1R antagonist currently used as a clinical drug for treating chemotherapy-related nausea and vomiting, have demonstrated that pharmacological inhibition of NK1R effectively reduces the growth of several tumor types such as neuroblastoma (NB). In a previous work, we demonstrated that a series of carbohydrate-based Aprepitant analogs, derived from either d-galactose or l-arabinose, have shown high affinity and NK1R antagonistic activity with a broad-spectrum anticancer activity and an important selectivity. In this new study, we explore the selective cytotoxic effects of these derivatives for the treatment of NB.

Synthesis and characterization of enantiopure chiral NH/SO palladium complexes.

A series of enantiopure chiral NH/SO palladium complexes have been synthesised with high yields by treating the corresponding -butylsulfinamide/sulfoxide derivatives with Pd(CHCN)Cl. The enantiopure chiral ligands were prepared by stereoselective addition of -butyl or phenyl methylsulfinyl carbanions to different -butylsulfinylimines. In all cases, coordination occurs with concomitant desulfinylation.

Biologically Relevant Micellar Nanocarrier Systems for Drug Encapsulation and Functionalization of Metallic Nanoparticles.

The preparation of new and functional nanostructures has received more attention in the scientific community in the past decade due to their wide application versatility. Among these nanostructures, micelles appear to be one of the most interesting supramolecular organizations for biomedical applications because of their ease of synthesis and reproducibility and their biocompatibility since they present an organization similar to the cell membrane. In this work, we developed micellar nanocarrier systems from surfactant molecules derived from oleic acid and tetraethylene glycol that were able to encapsulate and in vitro release the drug dexamethasone.

Carbohydrate-Based NK1R Antagonists with Broad-Spectrum Anticancer Activity.

NK1R antagonists, investigated for the treatment of several pathologies, have shown encouraging results in the treatment of several cancers. In the present study, we report on the synthesis of carbohydrate-based NK1R antagonists and their evaluation as anticancer agents against a wide range of cancer cells. All of the prepared compounds, derived from either d-galactose or l-arabinose, have shown high affinity and NK1R antagonistic activity with a broad-spectrum anticancer activity and an important selectivity, comparable to Cisplatin.

N-Isopropylsulfinylimines vs. N-tert-butylsulfinylimines in the stereoselective synthesis of sterically hindered amines: an improved synthesis of enantiopure (R)- and (S)-rimantadine and the trifluoromethylated analogues.

An improved fully stereoselective synthesis of both enantiomers of rimantadine and its trifluoromethylated analogues has been developed, using N-isopropylsulfinylimines as a starting chiral material, proving the superiority of the isopropyl group as a chiral inducer over the tert-butyl group in the case of hindered N-sulfinylimines.

"Sulfolefin": a mixed sulfinamido-olefin ligand in enantioselective rhodium-catalyzed addition of arylboronic acids to trifluoromethyl ketones.

Performing catalytic enantioselective carbon-carbon bond forming reactions, especially for the synthesis of tertiary carbinols, is one of the most challenging goals in modern asymmetric synthesis. Herein, we report an efficient enantioselective catalytic approach for the 1,2-addition of arylboronic acids to trifluoromethyl ketones affording tertiary trifluoromethyl-substituted alcohols with high yields and good enantioselectivities. The reported process uses as a catalyst precursor the shelf stable sulfinamido-olefin ligand 1, "sulfolefin", obtained on a multigram scale and in one step from a sugar derived sulfinate ester.

Flexible C2-symmetric bis-sulfoxides as ligands in enantioselective 1,4-addition of boronic acids to electron-deficient alkenes.

The application of acyclic C2-symmetric chelating bis-sulfoxide ligands in the Rh(I)-catalyzed enantioselective 1,4-addition of boronic acids to electron-deficient alkenes is reported. Among the acyclic ethane-bridged bis-sulfoxides tested, the ligand Ferbisox (11), bearing ferrocenyl moieties as substituents at the sulfinyl sulfurs, has exhibited the best results in terms of chemical yield (up to 96%) and enantioselectivity (up to 97% ee). The conjugate addition takes place smoothly in toluene at room temperature in short reaction times (typically 2 h).

Chiral sulfur derivatives in the allylation of acyl hydrazones: C(2)-symmetric bis-sulfinamides as enhanced chiral organic promoters.

Monosulfinamides and C(2)-symmetric bis-sulfinamides are convenient neutral chiral promoters in the allylation of acyl hydrazones, the nature of the spacer and the substituent at the sulfinyl sulfur are key elements for the enantioselectivity of the process.

Axial chirality control during Suzuki-Miyaura cross-coupling reactions: the tert-butylsulfinyl group as an efficient chiral auxiliary.

An efficient route to a new family of axially chiral biaryl ligands by a Suzuki-Miyaura cross-coupling reaction between ortho,ortho'-disubstituted aryl iodides bearing in ortho position a tert-butyl or p-tolylsulfinyl group and ortho-substituted phenyl boronic acids or esters is described. The comparison between the t-BuSO and p-TolSO groups as chiral controllers is reported. The modularity of the approach is demonstrated by the preparation of a variety of enantiopure axially chiral mixed S/N and S/P ligands.

N-isopropylsulfinylimines as useful intermediates in the synthesis of chiral amines: expeditive asymmetric synthesis of the calcimimetic (+)-NPS R-568.

An efficient and high-yielding approach for the asymmetric synthesis of calcimimetic (+)-NPS R-568 (1) has been developed. The key step of the synthesis is the highly diastereoselective addition of methyl Grignard to the (SS,E)-N-(3-methoxybenzylidene)-2-propanesulfinamide [5(S)], which afforded a single diastereoisomer in high yield in short reaction time.

C2-symmetric bissulfoxides as organocatalysts in the allylation of benzoyl hydrazones: spacer and concentration effects.

A comparative study on the allylation of a benzoyl hydrazone with allyl trichlorosilane using monosulfoxides, methylene-bridged C2-symmetric bissulfoxides, and ethylene-bridged C2-symmetric bissulfoxides shows that the enantioselectivity of the process is highly dependent on the spacer between the two sulfinyl sulfurs and the concentration of the reaction.

Enantioselective organocatalytic oxidation of functionalized sterically hindered disulfides.

[structure: see text]. The first study on enantioselective oxidation of functionalized sterically hindered disulfides is reported. This study shows that the Shi organocatalytic system using carbohydrate-derived ketone with oxone is superior to the Ellman-Bolm vanadium catalyst in terms of chemical yield and enantioselectivity.

The isopropylsulfinyl group: a useful chiral controller for the asymmetric aziridination of sulfinylimines and the organocatalytic allylation of hydrazones.

[reaction: see text] A comparative study shows that the isopropylsulfinyl group for which an enantiodivergent and highly diastereoselective approach is reported behaves better than the tert-butylsulfinyl and p-tolylsulfinyl groups, both in terms of reactivity and stereoselectivity in the Corey-Chaykovsky reaction of chiral sulfinylimines and the organocatalytic allylation of acyl hydrazones.