Diastereoselective Synthesis of Novel Benzofuran Derivatives by Euparin as a Natural Compound with DMAD in the Presence of Trialkyl Phosphite

An efficient, simple, and diastereoselective synthesis of novel benzofuran phosphonato ester derivatives has been achieved via a one‐pot three‐component reaction of euparin as a natural product, trialkyl phosphate, and dimethyl acetylenedicarboxylate (DMAD) in diethyl ether without using any catalyst at room temperature. NMR spectroscopic data and X‐ray crystallography analysis are in agreement with the anti arrangement for the two vicinal protons in the structures, and only one diastereoisomer (2S,3R) or (2R,3S) was obtained for the products. The advantage of our research is that this is the first report for the diastereoselective synthesis of phosphonato ester derivatives from a green natural product. This one‐pot reaction occurs in high yields with easy work‐up under mild conditions. All pure products were obtained by recrystallization from ethanol, and there was no need for column chromatography.     

An eco-friendly tandem tosylation/Ferrier N-glycosylation of amines catalyzed by Er(OTf)3 in 2-MeTHF

Er(OTf)₃ in 2-MeTHF provides a new and eco-friendly process for Ferrier glycosylation of sulfonamides and amino acids with various N-nucleophiles.The stereoselective synthesis of 2,3-unsaturated-N-pseudoglycals was carried out with 3,4,6-tri-O-acetyl-d-glucal and different nucleophiles affording good results in a short time.     

UNIQUAC correlation of liquid–liquid equilibrium in systems involving ionic liquids: The DFT–PCM approach. Part II

In this work, new UNIQUAC structural parameters r and q for the ionic liquids were determined by quantum chemistry calculations performed with the Gaussian 03 and GAMESS 7.1 packages, including the density functional theory (DFT) for the optimization of the structures and the polarizable continuum method (PCM) for the calculation of molecular areas and volumes. Data liquid–liquid equilibrium (LLE) of 41 ternary systems involving 15 different ionic liquids, comprising 379 experimental tie-lines, was correlated by the UNIQUAC model for the activity coefficient. The results, expressed by deviations between experimental and calculated compositions, are very satisfactory, with deviation values about 1.93%.     

Liquid–liquid equilibrium in ternary ionic liquid systems by UNIFAC: New volume,surface area and interaction parameters. Part I

Ternary liquid–liquid equilibria (LLE) data in systems involving ionic liquids has been investigated by several years, mainly due to the innovative role of ionic liquids as extraction solvents. The thermodynamic modeling of these systems has been performed almost invariably with the well-known NRTL model. In recent years, the UNIQUAC model has also been used, with structural parameters for ionic liquids determined either by empirical correlations or, more recently, through quantum mechanics calculations. In this work, the structural group volume and area parameters for the group-contribution UNIFAC method have been calculated for six ionic liquids following the quantum mechanics approach. The Density Functional Theory (DFT) was used to optimize the molecular geometry and the Polarizable Continuum Method (PCM) was used to calculate the area and volume. The obtained parameters were used to correlate LLE data for twenty-four ternary systems, totalizing 169 tie-lines. New interaction parameters were also estimated between the solvent and ionic liquid functional groups. The results are very satisfactory, with root mean square deviations between experimental and calculated compositions about 1.6%.     

Structural Diversity in the Self‐Assembly of Pseudopeptidic Macrocycles

The self‐assembling abilities of several pseudopeptidic macrocycles have been thoroughly studied both in the solid (SEM, TEM, FTIR) and in solution (NMR, UV, CD, FTIR) states. Detailed microscopy revealed large differences in the morphology of the self‐assembling micro/nanostructures depending on the macrocyclic chemical structures. Self‐assembly was triggered by the presence of additional methylene groups or by changing from para to meta geometry of the aromatic phenylene backbone moiety. More interestingly, the nature of the side chain also plays a fundamental role in some of the obtained nanostructures, thus producing structures from long fibers to hollow spheres. These nanostructures were obtained in different solvents and on different surfaces, thus implying that the chemical information for the self‐assembly is contained in the molecular structure. Dilution NMR studies (chemical shift and self‐diffusion rates) suggest the formation of incipient aggregates in solution by a combination of hydrogen‐bonding and π–π interactions, thus implicating amide and aryl groups, respectively. Electronic spectroscopy further supports the π–π interactions because the compounds that lead to fibers show large hypochromic shifts in the UV spectra. Moreover, the fiber‐forming macrocycles also showed a more intense CD signature. The hydrogen‐bonding interactions within the nanostructures were also characterized by attenuated total‐reflectance FTIR spectroscopy, which allowed us to monitor the complete transition from the solution to the dried nanostructure. Overall, we concluded that the self‐assembly of this family of pseudopeptidic macrocycles is dictated by a synergic action of hydrogen‐bonding and π–π interactions. The feasibility and geometrical disposition of these interactions finally render a hierarchical organization, which has been rationalized with a proposal of a model. The understanding of the process at the molecular level has allowed us to prepare hybrid soft materials.     

The first example of stereoselective self-assembly of a cryptand containing four asymmetric intracyclic phosphane groups

The rac stereoisomer of a novel cryptand containing two bridgehead nitrogen and four asymmetric phosphorus atoms in the 16-membered core cycle was obtained stereoselectively via the reaction of bis(mesitylphosphino)propane, formaldehyde, and meta-xylylenediamine in the course of a covalent self-assembly process.     

Tautomerism and microsolvation in 2-hydroxypyridine/2-pyridone

The Fourier transform microwave spectra of the hydrated forms of the tautomeric pair 2-pyridinone/2-hydroxypyridine (2PO/2HP) have been investigated in a supersonic expansion. Three hydrated species, 2PO-H?O, 2HP-H?O, and 2PO-(H?O)?, have been observed in the rotational spectrum. Each molecular complex was confidently identified by the features of the 1?N quadrupole hyperfine structure of the rotational transitions. The presence of water affects the tautomeric equilibrium -N═C(OH)- ? -NH-C(═O)-, which is shifted to the enol form for the bare molecules 2PO/2HP but to the keto tautomer for the hydrated forms.     

General correlation model for some physical properties of saturated pure fluids

In this work, we use a general expression to accurately correlate the liquid density, the vaporization enthalpy, the surface tension, and the isobaric heat capacity of a saturated liquid versus temperature along the whole coexistence curve. The general expression used is the same for the four thermodynamic properties, and uses both critical and triple point values as reference. As representative examples of the use of the model, results are given for a set of 22 pure substances. We find that this general expression correlates the data with smaller or similar overall deviations when compared with other published models whose number of coefficients are the same or greater.     

Approximation of the inductionless MHD problem using a stabilized finite element method

In this work, we present a stabilized formulation to solve the inductionless magnetohydrodynamic (MHD) problem using the finite element (FE) method. The MHD problem couples the Navier–Stokes equations and a Darcy-type system for the electric potential via Lorentz’s force in the momentum equation of the Navier–Stokes equations and the currents generated by the moving fluid in Ohm’s law. The key feature of the FE formulation resides in the design of the stabilization terms, which serve several purposes. First, the formulation is suitable for convection dominated flows. Second, there is no need to use interpolation spaces constrained to a compatibility condition in both sub-problems and therefore, equal-order interpolation spaces can be used for all the unknowns. Finally, this formulation leads to a coupled linear system; this monolithic approach is effective, since the coupling can be dealt by effective preconditioning and iterative solvers that allows to deal with high Hartmann numbers.