Synthesis and catalytic activity of a fluorous-tagged TEMPO radical

A fluorous-tagged TEMPO radical has been prepared and its catalytic activity in the chemoselective oxidation of alcohols to carbonyl compounds has been investigated. The new fluorous radical proved to be an efficient, selective and easily recoverable catalyst, which can be conveniently used in standard organic solvents and then isolated and recycled by fluorous liquid-liquid extraction.     

Total synthesis of (±)-cyclooroidin

The first total synthesis of (±)-cyclooroidin, a member of the pyrrole-imidazole alkaloid family recently isolated from the sponge Agelas oroides in optically pure form, is described. The synthesis was achieved in nine linear steps, with an overall yield of 10%. Key step was a Wolff bromoketone synthesis performed on the intermediate longamide B.     

Aldol condensations over reconstructed Mg-Al hydrotalcites: structure-activity relationships related to the rehydration method

Two different rehydration procedures in the liquid or gas phase have been applied to reconstruct mixed oxides derived from calcined hydrotalcite-like materials to be used as catalysts for aldol condensation reactions. The as-synthesized hydrotalcite, its decomposition product, as well as the reconstructed solids upon rehydration were characterized by XRD, N(2) adsorption, He pycnometry, FTIR, SEM, TEM, (27)Al MAS-NMR and CO(2)-TPD (TPD=temperature-programmed desorption). Compared to the Mg-Al mixed oxide rehydrated in the gas phase (HT-rg), that rehydrated in the liquid phase (HT-rl) exhibits a superior catalytic performance with respect to the aldol condensation of citral with ketones to yield pseudoionones and in the self-aldolization of acetone. The textural properties of HT-rl and HT-rg differ strongly and determine the catalytic behavior. A memory effect led to a higher degree of reconstruction of the lamellar structure when the mixed oxide was rehydrated in the gas phase rather than in the liquid phase, although liquid-phase rehydration under fast stirring produced a surface area that was 26 times greater. This contrasts to typical statements in the literature claiming a higher degree of reconstruction in the presence of large amounts of water in the medium. CO(2)-TPD shows that the number of OH(-) groups and their nature are very similar in HT-rg and HT-rl, and cannot explain the markedly different catalytic behavior. Accordingly, only a small fraction of the available basic sites in the rehydrated samples is active in liquid-phase aldol condensations. Our results support the model in which only basic sites near the edges of the hydrotalcite platelets are partaking in aldol reactions. Based on this, reconstructed materials with small crystallites (produced by exfoliation during mechanical stirring), that is, possessing a high external surface area, are beneficial in the reactions compared to larger crystals with a high degree of intraplatelet porosity.     

A highly stable short alpha-helix constrained by a main-chain hydrogen-bond surrogate

Herein we describe a strategy for the preparation of artificial alpha-helices involving replacement of one of the main-chain hydrogen bonds with a covalent linkage. To mimic the C=O...H-N hydrogen bond as closely as possible, we envisioned a covalent bond of the type C=X-Y-N, where X and Y are two carbon atoms connected through an olefin metathesis reaction. Our results demonstrate that the replacement of a hydrogen bond between the i and i + 4 residues at the N-terminus of a short peptide with a carbon-carbon bond results in a highly stable constrained alpha-helix at physiological conditions as indicated by CD and NMR spectroscopies. The advantage of this strategy is that it allows access to short alpha-helices with strict preservation of molecular recognition surfaces required for biomolecular interactions.     

Template evaporation method for controlling anatase nanocrystal size in ordered macroporous TiO2

The importance of pure-phase titanium oxide materials as catalysts, sensors, and photonic band-gap materials has been growing steadily. Recently, more attention has been focused on nanostructured titanium oxide showing controlled and periodic porosity on a nanometric scale. The nanocrystal size control of porous nanostructured titanium oxide in an anatase form is a crucial step for the organic template method. Simple template removal by evaporation in an inert atmosphere is reported in this article and compared with the calcination technique usually reported in the literature. The proposed method allows the formation of a double-porous (macro and meso) anatase phase. We demonstrate that it highly preserves the macropore order into a titanium oxide material and induces narrowly dispersed mesopores by controlling the nano-crystal size that is kept around 6 nm. For the proposed method, polystyrene beads are particularly suitable as templates, being evaporated in the temperature range of anatase existence. The final high surface area makes the materials appealing for applications as photocatalysts or sensors.     

A New Technique for Preserving Conservation Laws

Foundations of Computational Mathematics - This paper introduces a new symbolic-numeric strategy for finding semidiscretizations of a given PDE that preserve multiple local conservation laws. We...     

Enantiomeric resolution of anti-HIV agents on a cellulose derivative chiral stationary phase

Summary Anti-HIV enantiomeric 1H, 3H-thiazolo[3, 4-a] benzimidazoles have been stereospecifically analyzed by elution on a column of cellulose tris-(4-methyl-phenylbenzoate)ester adsorbed on macroporous silica (Chiralcel^R OJ).The enantiomeric resolution of the compounds examined is linked to a complex and competitive contribution of different factors.     

Influence of organic modifier and temperature on the enantiomeric separation of γ-lactams by HPLC

Summary A high-performance liquid chromatographic method is reported for the resolution of the enantiomers of a series of fused -lactams (2,7-diaza-3-oxo[3.3.0]octan-6-ones) with probable anti-HIV and anticancer activity. Resolution was achieved on a Chiralcel^® OD column, cellulose tris-(3,5-dimethylphenyl carbamate) adsorbed on macroporous silica gel; mixtures ofn-hexane and isopropyl alcohol in different proportions were used as the mobile phase. The analysis was studied at different temperatures.     

Synthesis and structural characterization of isomeric coumarino‐1,2‐oxaphosphole derivatives

The coumarino‐[3,4‐c]‐3H‐10‐methyl‐2‐oxo‐2‐phenyl‐1,2‐oxaphosphole was prepared by the addition of PhPCl₂ to 3‐acetylcoumarin in the presence of acetic anhydride. Its conversion to the isomeric coumarino‐[3,4‐c]‐9H‐9‐methyl‐2‐oxo‐2‐phenyl‐1,2‐oxaphosphole was studied in different reaction conditions. The structures of the two isomers were determined by X‐ray crystallography and by ab initio molecular orbital calculations.     

Studies on the Enzymatic Acylation of Quinic Acid,Shikimic Acid,Shikimic Acid,and Their Derivatives in Organic Solvents

Quinic acid ( 1a ), shikimic acid ( 2 ), and their derivatives were acylated in organic solvents by several lipases and by the protease subtilisin Carlsberg. The most satisfactory results were obtained with methyl (or benzyl) quinate ( 7a (or 8a )) and lipase from Chromobacterium viscosum adsorbed on Celite, which showed an overshelming preference towards the acylation of OH–C(4). Under optimized conditions, the syntehtically useful 4-O -acetylquinate 8d was isolated in ca. 90% yield. On the other hand, acylation of methyl shikimate ( 10a ) showed no regioselectivity with any of the enzymes tested. A possible rationale for the different behavior of Chromobacterium viscosum lipase towards 7a and 10a is given, comparing the conformations of these two molecules, as deducted from ¹H-NMR and molecular-mechanics calculation.