Asymmetric Oxidation of Enol Derivatives to α-Alkoxy Carbonyls Using Iminium Salt Catalysts: A Synthetic and Computational Study.

We report herein the first examples of asymmetric oxidation of enol ether and ester substrates using iminium salt organocatalysis, affording moderate to excellent enantioselectivities of up to 98% ee for tetralone-derived substrates in the α-hydroxyketone products. A comprehensive density functional theory study was undertaken to interpret the competing diastereoisomeric transition states in this example in order to identify the origins of enantioselectivity. The calculations, performed at the B3LYP/6-31G(D) level of theory, gave good agreement with the experimental results, in terms of the magnitude of the effects under the specified reaction conditions, and in terms of the preferential formation of the ( R)-enantiomer. Just one of the 30 characterized transition states dominates the enantioselectivity, which is attributed to the adoption of an orientation relative to stereochemical features of the chiral controlling element that combines a CH-π interaction between a CH2 group in the substrate and one of the aromatic rings of the biaryl section of the chiral auxiliary with a good alignment of the acetoxy group with the other biaryl ring, and places the smallest substituent on the alkene (a hydrogen atom) in the most sterically hindered position.

Microwave-Assisted Synthesis of Some Potential Bioactive Imidazolium-Based Room-Temperature Ionic Liquids.

An environmentally-friendly and easy synthesis of a series of novel functionalized imidazolium-based ionic liquids (ILs) is described under both the conventional procedure and microwave irradiation. The structures of newly synthesized room-temperature ionic liquids (RTILs) were established by different spectral analyses. All ILs (1⁻14) were screened for their in vitro antimicrobial activity against a panel of clinically isolated bacteria. The results of the minimum inhibitory concentration (MIC) and the minimum bactericidal concentration (MBC) showed that some of the tested ILs are very promising anti-bacterial agents especially those containing an alkyl chain with a phenyl group (most notably 1, 2, 12, and 13).

An efficient, mild and metal free l-proline catalyzed construction of fused pyrimidines under microwave conditions in water.

One-pot condensation of 4-hydroxy coumarins, aldehydes and urea/thiourea to build C-C and C-N bonds is described. Fused pyrimidines have been synthesized under mild reaction conditions using l-proline. The protocol has been performed rapidly and efficiently in water under metal free conditions. Heterocyclic derivatives have been synthesized using the present methodology and avoid the use of hazardous solvents over conventional organic solvents. A proposed mechanism could be established for three component reactions. The present study reveals the first case in which l-proline has been explored as a homogeneous catalyst in the synthesis of fused pyrimidines in water under microwave irradiation. This synthesis involves simple workup and acceptable efficiency. The most notable feature of this protocol is the ability of the catalyst to influence asymmetric induction in the reaction.

Sustainable Synthesis and Characterization of Ni-Al-Containing Double-Layered Nanocatalysts and Their Catalytic Activity.

Sustainable synthesis of Ni-Al double-layered catalysts by the coprecipitation method is described. Synthesized double-layered catalysts have been characterized by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared, and thermogravimetric analyses, which confirmed a hydrotalcite-like structure. In addition, the impact of aging time and temperature on the activity of catalyst has been investigated. Furthermore, it has been confirmed by SEM and TEM analyses that the recovered catalyst has retained its structure. It has also been observed that the prepared material has potency to catalyze the reaction without loss in the yield. To explore the reactivity of the material, the catalyst has been examined in the synthesis of N-(2-hydroxyphenyl)benzamide under solvent-free conditions. The overall process afforded the product with high purity and high yields within short time.

Metal-Free Construction of Fused Pyrimidines via Consecutive C-C and C-N Bond Formation in Water.

A facile and efficient protocol has been developed for mild construction of fused pyrimidines via l-proline-catalyzed reaction of 4-hydroxy coumarins, aldehydes, and 2-aminobenzothiazoles/urea. The reaction has been carried out rapidly and efficiently in water under mild and metal-free conditions. Current etiquette has efficiently synthesized the heterocycles and avoids the use of hazardous solvents over conventional organic solvents. A plausible reaction mechanism has been established in this study. This study represents the first case in which l-proline as a homogeneous catalyst has been explored in the synthesis of fused pyrimidines in water in view of simple procedure and acceptable efficiency. This method gives the target product in excellent yield with ease of workup.

One-pot facile and mild construction of densely functionalized pyrimidines in water via consecutive C-C and C-S bonds formation.

Fused pyrimidines composed of alternating heteroatoms and a pyrimidine moiety were synthesized efficiently using readily available starting material 4-hydroxycoumarin, aromatic aldehydes, and urea/thiourea at room temperature. Acid, metal salts, and surfactants were screened for their influence on catalytic activity in three-component reactions and sodium lauryl sulphate (SLS) was used as the best catalyst with different concentrations. Screening results of catalyst loading from our investigation showed that good to excellent yields were obtained with 10 mol%. Our method efficiently synthesized heterocycles and avoided the use of hazardous solvents and conventional organic solvents. Our procedure which involves a surfactant is operationally simple, environmentally benign, has excellent yields, short reaction times, and synthetically is as efficient as conventional procedures using organic solvents.