Enzyme Promiscuity as a Remedy for the Common Problems with Knoevenagel Condensation

A new protocol based on lipase-catalyzed tandem reaction toward α,β-enones/enoesters is presented. For the synthesis of the desired products the tandem process based on enzyme-catalyzed hydrolysis and Knoevenagel reaction starting from enol acetates and aldehyde is developed. The relevant impact of the reaction conditions including organic solvent, enzyme type, and temperature on the course of the reaction was revealed. It was shown that controllable release of the active methylene compound from the corresponding enol carboxylate ensured by enzymatic reaction diminishes significantly the formation of the unwanted co-products. Furthermore, this protocol was extended by including a second tandem chemoenzymatic transformation engaging various aldehyde precursors. After a careful optimization of the reaction conditions, the target products were obtained with yields up to 86 % and with excellent E/Z-selectivity.     

Synthesis,crystal structure and conformational analysis of an unexpected [1,5]dithiocine product of aminopyridine and thiovanillin

The condensation reaction of 2‐mercapto‐3‐methoxybenzaldehyde with 3‐aminopyridine afforded an unexpected N‐alkylated [1,5]dithiocine instead of the N‐salicylideneaniline. The proposed mechanism for this condensation involves a strong intramolecular hydrogen bond between the thiol and the amine groups, leading to a second condensation. The corresponding product, i.e. 4,10‐dimethoxy‐13‐(pyridin‐3‐yl)‐6H,12H‐6,12‐epiminodibenzo[b,f][1,5]dithiocine methanol 0.463‐solvate, C₂₁H₁₈N₂O₂S₂·0.463CH₃OH, was characterized by single‐crystal X‐ray diffraction analysis. The supramolecular structure shows π–π stacking and S…S interactions in the crystal packing. Within the asymmetric unit, two geometries of the N atom are observed. Although a planar geometry should be expected, a pyramidal one is observed due to the crystal packing. The presence of the two geometries was further supported by density functional theory (DFT) calculations that show an electronic energy difference of less than 2 kJ mol^?1 between the two conformers.     

A new class of stereoregular vinylene‐arylene copolymers with double‐decker silsesquioxane in the main chain

A synthesis of a new macromolecular class of vinylene‐arylene copolymers with double‐decker silsesquioxane in the main chain is presented. Two transition‐metal‐catalyzed processes, which is silylative‐coupling copolycondensation (SCC) and ADMET copolymerization of divinyl‐substituted double‐decker silsesquioxanes (DDSQ‐2SiVi) with selected diolefins, are reported to be highly efficient tools for the formation of stereoregular copolymers containing DDSQ‐silylene‐vinylene‐arylene units. The copolymeric products are studied in terms of their structural, thermal, and mechanical properties. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1044–1055     

Generalization of the Kelvin equation for arbitrarily curved surfaces

Capillary condensation, which takes place in confined geometries, is the first-order vapor-to-liquid phase transition and is explained by the Kelvin equation, but the equation's applicability for arbitrarily curved surface has been long debated and is severe problem. Recently, we have proposed generic dynamic equations for moving surfaces. Application of the equations to the vapor/fluid interfaces in chemical equilibrium conditions nearly trivially solves the generalization problem for the Kelvin equation. The equations are universally true for any surfaces: atomic, molecular, micro or macro scale, real or virtual, Riemannian or pseudo-Riemannian, active or passive.     

Sustainable synthesis of quinolines (pyridines) catalyzed by a cheap metal Mn(I)-NN complex catalyst

This study represents the first example of a bidentate phosphine-free manganese(I)-NN complex catalyst for the synthesis of quinolines (pyridines) through acceptorless dehydrogenative condensation of various secondary alcohols with amino alcohols. The coupling reactions occurred at 3 mol% catalyst loading and 110°C, and tolerated diverse functional groups. Moderate to excellent yields ranging from 45% to 89% were achieved after 12 hr of reaction. The present protocol provides a concise and environmentally friendly method for the construction of heterocyclic compounds.     

Co-hydrolysis and Seed-Induced Synthesis of Basic Mesoporous ZSM-5 Zeolites with Enhanced Catalytic Performance

For zeolite catalysts, the regulation of active site and pore structure plays an important role in the enhancement of their catalytic performance. In this work, a one-pot and organic template-free co-regulation route is proposed to straightforwardly synthesize basic mesoporous ZSM-5 zeolites with adjustable alkaline-earth metal species. The synthesis pathway combines two decisive strategies: 1) the seed-induced interface assembly growth method and 2) the acidic co-hydrolysis/condensation of aluminosilicate species and alkaline-earth metal (e.g., Mg, Ca, Sr, or Ba) sources. It is interesting that the mesoporous structure was self-evolved through particle-attached seed-interfacial crystallization without the assistance of any template. Meanwhile, the incorporation of alkaline-earth metals species is homogeneous and highly dispersed in the solid products during the whole crystallization process, and finally generate the superior basicity. Catalysis tests of the as-synthesized samples displayed their novel performance in the typical base reaction of Knoevenagel condensation, even for bulky substrates owing to the enhanced diffusion arising from the meso/microporous network. This finding opens new possibilities for facile, cost-effective, and environmentally friendly synthesis of mesoporous high-silica zeolites with tunable acid/base properties, and deepens our understanding of the particle-attached crystallization.     

Synthesis and biological evaluation of novel phane-structured diazacrowns containing γ-piperidone and pyridine rings

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Collective Strategy Condensation: When Envy Splits Societies

Human societies are characterized by three constituent features, besides others. (A) Options, as for jobs and societal positions, differ with respect to their associated monetary and non-monetary payoffs. (B) Competition leads to reduced payoffs when individuals compete for the same option as others. (C) People care about how they are doing relatively to others. The latter trait—the propensity to compare one’s own success with that of others—expresses itself as envy. It is shown that the combination of (A)–(C) leads to spontaneous class stratification. Societies of agents split endogenously into two social classes, an upper and a lower class, when envy becomes relevant. A comprehensive analysis of the Nash equilibria characterizing a basic reference game is presented. Class separation is due to the condensation of the strategies of lower-class agents, which play an identical mixed strategy. Upper-class agents do not condense, following individualist pure strategies. The model and results are size-consistent, holding for arbitrary large numbers of agents and options. Analytic results are confirmed by extensive numerical simulations. An analogy to interacting confined classical particles is discussed.     

Ionic liquid-functional MCM-41 as a high effective catalyst for the synthesis of isatylidene malononitrile via Knoevenagel condensation

Ionic liquid functional MCM-41 was synthesized, characterized and used as heterogeneous catalyst for the Knoevenagel condensation of isatins with malononitrile. A series of corresponding isatylidene malononitrile were obtained in high isolated yield (96–99%) at room temperature in a short time. The heterogeneous catalyst can be easily recovered by centrifugation and showed almost no loss of activity over 10 recycle experiments. At the same time, the gram-scale experiments showed excellent yields and provided a highly effective method for scale up applications.     

Lewis Acid Catalyzed Condensation–Cyclization Cascade: Direct Synthesis of Di/Trifluoromethyl‐1,2,3,4‐tetrahydroquinazolines

Condensed heterocycles such as quinazolines constitute the framework of many promising drugs. The great impact of the dramatic fluorine effect in pharmaceuticals prompted a great surge in the quest for fluorinated drug design resulting in over 20 % fluorine‐containing drugs in the market today. Therefore, finding an efficient and cost‐effective method for the direct synthesis of fluorine‐tagged quinazoline systems is of great significance in the pharmaceutical arena. For the first time, a one‐pot sequential condensation–cyclization reaction to form selectively the difluoro/trifluoromethylated tetrahydroquinazolines from simple components difluoro/trifluoroacetaldehyde hemiacetal and aromatic amines is reported. Our recent studies using difluoro/trifluoroacetaldehyde hemiacetal as simple and elegant difluoro/trifluoromethyl synthons and metal triflates such as gallium triflate as safe and stable Lewis acid catalysts led us to this direct synthesis protocol for the expedient and convenient synthesis of fluorinated quinazolines. DFT calculations at PCM/B3LYP/6‐31++G** were carried out for evaluating a possible reaction mechanism for this cyclization. According to the DFT calculations, product stereochemistry is thermodynamically driven, favoring the cis isomer as the major product, which is also confirmed experimentally.