Unprecedented Diastereoselective Arylogous Michael Addition of Unactivated Phthalides

The first highly enantioselective arylogous Michael reaction (AMR) of 3-unsubstituted phthalides has been described. This phase-transfer methodology, which uses catalytic amounts of KOH/18-crown-6 catalyst in mesitylene in the presence of N,O-bis(trimethylsilyl)acetamide (BSA), gives access to a broad range of 3-monosubstituted phthalides with high levels of syn diastereoselectivity and good yields, starting from 3-unsubstituted derivatives and diverse α,β-unsaturated carbonyl compounds. The reaction also applies to unactivated 3-alkyl phthalides to afford 3,3-dialkyl derivatives. A plausible mechanism has been suggested. DFT analysis of possible transition states gives a rationale of the high syn diastereoselectivity observed and its correlation with the solvent's dielectric constant.     

Increasing Complexity: A Practical Synthetic Approach to Three-Dimensional,Cyclic Sulfoximines and First Insights into Their in Vitro Properties

A short synthetic approach with broad scope to access five- to seven-membered cyclic sulfoximines in only two to three steps from readily available thiophenols is reported. Thus, simple building blocks were converted to complex molecular structures by a sequence of S-alkylation and one-pot sulfoximine formation, followed by intramolecular cyclization. Seventeen structurally diverse cyclic sulfoximines were prepared in high overall yields. In vitro evaluation of these underrepresented, three-dimensional, cyclic sulfoximines with respect to properties relevant to medicinal chemistry did not reveal any intrinsic flaw for application in drug discovery.     

Multimetallic Oxynitrides Nanoparticles for a New Generation of Photocatalysts

A versatile synthetic strategy for the preparation of multimetallic oxynitrides has been designed and here exemplarily discussed considering the preparation of nanoscaled zinc–gallium oxynitrides and zinc–gallium–indium oxynitrides, two important photocatalysts of new generation, which proved to be active in key energy related processes from pollutant decomposition to overall water splitting. The synthesis presented here allows the preparation of small nanoparticles (less than 20 nm in average diameter), well-defined in size and shape, yet highly crystalline and with the highest surface area reported so far (up to 80 m² g⁻¹). X-ray diffraction studies show that the final material is not a mixture of single oxides but a distinctive compound. The photocatalytic properties of the oxynitrides have been tested towards the decomposition of an organic dye (as a model reaction for the decomposition of air pollutants), showing better photocatalytic performances than the corresponding pure phases (reaction constant 0.22 h⁻¹), whereas almost no reaction was observed in absence of catalyst or in the dark. The photocatalysts have been also tested for H₂ evolution (semi-reaction of the water splitting process) with results comparable to the best literature values but leaving room for further improvement.     

Highly Enantioselective Catalytic Kinetic Resolution of α-Branched Aldehydes through Formal Cycloaddition with Homophthalic Anhydrides

A new catalytic methodology was developed to promote an efficient one-pot kinetic resolution of racemic aldehydes with selectivity (s*) of up to 91 (99:1 d.r., >99 % ee) in a cycloaddition reaction with enolizable anhydrides to afford dihydroisocoumarin products (a core prevalent in natural products and molecules of medicinal interest) containing three contiguous stereocentres.     

On idempotents of a class of commutative rings

Abstract

In the present work, a procedure for determining idempotents of a commutative ring having a sequence of ideals with certain properties is presented. As an application of this procedure, idempotent elements of various commutative rings are determined. Several examples are included illustrating the main results.     

Surfactant effect on electrochemical-induced synthesis of α-Ni(OH)2

Nickel hydroxide films were electrosynthesized in the presence of different diluted surfactant solutions by galvanostatic electroprecipitation. Lamellar α-Ni(OH)₂ films are obtained using cationic surfactant cetyltrimethylammonium bromide (CTAB), anionic surfactant sodium dodecyl sulfate (SDS), and also neutral surfactant Tween® 80. The films were structurally and morphologically characterized by X-ray diffraction, thermal gravimetric analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy, and electrochemically by cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM). The results evidenced that SDS remains intercalated between the lamellae of α-Ni(OH)₂. Albeit the presence of CTAB and Tween® 80, it was noticed in FTIR spectra that the surfactants did not intercalate. The morphology was affected by the presence of different surfactants. All studied surfactants displaced the oxidation potential (E _O) of Ni²⁺/Ni³⁺ process to less positive values. Also, the presence of surfactants improved the electrode charge efficiency and the charge response for the same number of moles of nickel ions deposited. The ratio of the charge and frequency change is 4.4 times bigger for films deposited with SDS when compared with pure α-Ni(OH)₂ films.