Organocatalytic asymmetric direct vinylogous Michael addition of α,β-unsaturated γ-butyrolactam to nitroolefins

The first organocatalytic enantioselective direct vinylogous Michael reaction of α,β-unsaturated γ-butyrolactam to nitroolefins is developed using cinchona alkaloids as the catalysts. Both product enantiomers are accessible with moderate to good enantioselectivity.

Organocatalytic asymmetric direct vinylogous Michael addition of alpha,beta-unsaturated gamma-butyrolactam to nitroolefins

The first organocatalytic enantioselective direct vinylogous Michael reaction of alpha,beta-unsaturated gamma-butyrolactam to nitroolefins is developed using cinchona alkaloids as the catalysts. Both product enantiomers are accessible with moderate to good enantioselectivity.

2,3-Unsaturated enoses. A Pummerer rearrangement route to sugar vinyl sulfides and synthesis of 3-deoxy-3-alkyl/arylsulfinyl pyranosides

A Pummerer rearrangement of 2,3-dideoxy-3-alkyl/arylsulfinyl-arabino-hexopyranosides is reported. Treatment of sulfinyl-arabino-hexopyranoside derivatives, obtained through oxidation of the corresponding thio-derivatives, with trifluoroacetic anhydride (TFAA)/pyridine led to a facile formation of 2,3-dideoxy-3-alkyl/arylthio-hex-2-enopyranosides. Upon conversion of sugar vinyl sulfides to vinyl sulfoxides, conjugate addition reactions were conducted with alkoxides, to afford 3-deoxy-3-alkyl/arylsulfinyl pyranosides, in the manno-configuration exclusively. Whereas the conjugate addition reaction did not proceed with ether protecting groups, ester protecting groups and free hydroxyl groups in the sugar vinyl sulfoxide permitted the reaction. (C) 2012 Elsevier Ltd. All rights reserved.

Direct conversion of calcium carbonate to C-1-C-3 hydrocarbons

With the objective of investigating the direct conversion of inorganic carbonates such as CaCO3 to hydrocarbons, assisted by transition metal ions, we have carried out studies on CaCO3 in an intimate admixture with iron oxides (FeCaCO) with a wide range of Fe/Ca mole ratios (x), prepared by co-precipitation. The hydrogen reduction of FeCaCO at 673 K gives up to 23% yield of the hydrocarbons CH4, C2H4, C2H6 and C3H8, leaving solid iron residues in the form of iron metal, oxides and carbide particles. The yield of hydrocarbons increases with x and the conversion of hydrocarbons occurs through the formation of CO. While the total yield of hydrocarbons obtained by us is comparable to that in the Fischer-Tropsch synthesis, the selectivity for C-2-C-3 hydrocarbons reported here is noteworthy.

Facial selectivities in the nucleophilic additions of 2,3-unsaturated 3-arylsulfinyl pyranosides

2,3-Unsaturated 3-arylsulfinyl pyranosides undergo nucleophilic additions at C-2, with facial selectivities depending on the nucleophile and the substituent on sulfinyl sulfur. The reactions of such sugar vinyl sulfoxides lead to the addition of nucleophile preferring an axial orientation at C-2, with concomitant formation of an allylic bond at C-3 to C-4. This trend in the addition pattern is observed for primary amine, carbon and sulfur nucleophiles, whereas secondary amines prefer an equatorial addition at C-2. The effect of p-tolylthio-versus (p-isopropylphenyl)thio vinyl sulfoxide is that the equatorial nucleophilic addition is preferred even more with the latter vinyl sulfoxide. (C) 2013 Published by Elsevier Ltd.

Synthesis of substituted nitroolefins: a copper catalyzed nitrodecarboxylation of unsaturated carboxylic acids

A novel, mild and convenient method for the nitrodecarboxylation of substituted cinnamic acid derivatives to their nitroolefins is achieved using a catalytic amount of CuCl (10 mol%) and tert-butyl nitrite (2 equiv.) as a nitrating agent in the presence of air. This reaction provides a useful method for the synthesis of beta,beta-disubstituted nitroolefin derivatives, which are generally difficult to access from other conventional methods. Additionally, this reaction is selective as the E-isomer of the acid derivatives furnishes the corresponding E-nitroolefins. One more salient feature of the method is, unlike other methods, no metal nitrates or HNO3 are employed for the transformation.

Copper-Catalyzed Decarboxylative Sulfonylation of alpha,beta-Unsaturated Carboxylic Acids

Copper-catalyzed, ligand-promoted decarboxylative coupling of readily available a,fi-unsaturated acids with sodium aryl sulfinates is presented. This method provides a new avenue for the synthesis of vinyl sulfones via a decarboxylative radical coupling strategy by employing a catalytic amount of Cu(ClO4)(2)center dot 6H(2)O, TBHP in decane as an oxidant, and 1,10-phenanthroline as a ligand. The salient feature of this method is that it furnishes exclusively the (E)-isomer.

Role of degree of saturation in denitrification of unsaturated sand specimens

Nitrate contamination of groundwater arises from anthropogenic activities, such as, fertilizer and animal manure applications and infiltration of wastewater/leachates. During migration of wastewater and leachates, the vadose zone (zone residing above the groundwater table), is considered to facilitate microbial denitrification. Particle voids in vadose zone are deficient in dissolved oxygen as the voids are partially filled by water and the remainder by air. Discontinuities in liquid phase would also restrict oxygen diffusion and therefore facilitate denitrification in the vadose/unsaturated soil zone. The degree of saturation of soil specimen (S (r)) quantifies the relative volume of voids filled with air and water. Unsaturated specimens have S (r) values ranging between 0 and 100 %. Earlier studies from naturally occurring nitrate losses in groundwater aquifers in Mulbagal town, Kolar District, Karnataka, showed that the sub-surface soils composed of residually derived sandy soil; hence, natural sand was chosen in the laboratory denitrification experiments. With a view to understand the role of vadose zone in denitrification process, experiments are performed with unsaturated sand specimens (S (r) = 73-90 %) whose pore water was spiked with nitrate and ethanol solutions. Experimental results revealed 73 % S (r) specimen facilitates nitrate reduction to 45 mg/L in relatively short durations of 5.5-7.5 h using the available natural organic matter (0.41 % on mass basis of sand); consequently, ethanol addition did not impact rate of denitrification. However, at higher S (r) values of 81 and 90 %, extraneous ethanol addition (C/N = 0.5-3) was needed to accelerate the denitrification rates.

Synthesis of Azepino4,5-b]indolones by an Intramolecular Cyclization of Unsaturated Tryptamides

A facile general route for the synthesis of azepino4,5-b]indolones is presented. The strategy involves a Bronsted acid assisted intramolecular cyclization of unsaturated tryptamides. The methodology developed has been applied to the synthesis of the ABCD tetracyclic core of the natural product tronocarpine.

A coat of many scents: Cuticular hydrocarbons in multitrophic interactions of fig wasps with ants

The fig fig wasp system of Ficus racemosa constitutes an assemblage of galler and parasitoid wasps in which tritrophic interactions occur. Since predatory ants (Oecophylla smaragdina and Technomyrmex albipes) or mostly trophobiont-tending ants (Myrmicaria brunnea) were previously shown to differentially use volatile organic compounds (VOCs) from figs as proximal cues for predation on fig wasps, we examined the response of these ants to the cuticular hydrocarbons (CHCs) of the wasps. CHC signatures of gallers were distinguished from those of parasitoids by the methyl-branched alkanes 5-methylpentacosane and 13-methylnonacosane which characterised trophic group membership. CHC profiles of wasp predator and wasp prey were congruent suggesting that parasitoids acquire CHCs from their prey; the CHC composition of the parasitoid Apocrypta sp 2 clustered with that of its galler host Apocryptophagus fusca, while the CHC profile of the parasitoid Apocryptophagus agraensis clustered with its galler prey, the fig pollinator Ceratosolen fusciceps. In behavioural assays with ants, parasitoid CHC extracts evoked greater response in all ant species compared to galler extracts, suggesting that parasitoid CHC extracts contain more elicitors of ant behaviour than those of plant feeders. CHCs of some wasp species did not elicit significant responses even in predatory ants, suggesting chemical camouflage. Contrary to earlier studies which demonstrated that predatory ants learned to associate wasp prey with specific fig VOCs, prior exposure to fig wasp CHCs did not affect the reaction of any ant species to these CHCs. (C) 2015 Elsevier Masson SAS. All rights reserved.

Modeling the co-transport of viruses and colloids in unsaturated porous media

A mathematical model is developed to simulate the co-transport of viruses and colloids in unsaturated porous media under steady-state flow conditions. The virus attachment to the mobile and immobile colloids is described using a linear reversible kinetic model. Colloid transport is assumed to be decoupled from virus transport; that is, we assume that colloids are not affected by the presence of attached viruses on their surface. The governing equations,are solved numerically using an alternating three-step operator splitting approach. The model is verified by fitting three sets of experimental data published in the literature: (1) Syngouna and Chrysikopoulos (2013) and (2) Walshe et al. (2010), both on the co-transport of viruses and clay colloids under saturated conditions, and (3) Syngouna and Cluysikopoulos (2015) for the co-transport of viruses and clay colloids under unsaturated conditions. We found a good agreement between observed and fitted breakthrough curves (BTCs) under both saturated and unsaturated conditions. Then, the developed model was used to simulate the co-transport of viruses and colloids in porous media under unsaturated conditions, with the aim of understanding the relative importance of various processes on the co-transport of viruses and colloids in unsaturated porous media. The virus retention in porous media in the presence of colloids is greater during unsaturated conditions as compared to the saturated conditions due to: (1) virus attachment to the air-water interface (AWI), and (2) co-deposition of colloids with attached viruses on its surface to the AWL A sensitivity analysis of the model to various parameters showed that the virus attachment to AWI is the most sensitive parameter affecting the BTCs of both free viruses and total mobile viruses and has a significant effect on all parts of the BTC. The free and the total mobile viruses BTCs are mainly influenced by parameters describing virus attachment to the AIM, virus interaction with mobile and immobile colloids, virus attachment to solid-water interface (SWI), and colloid interaction with SWI and AWL The virus BTC is relatively insensitive to parameters describing the maximum adsorption capacity of the AWI for colloids, inlet colloid concentration, virus detachment rate coefficient from the SW!, maximum adsorption capacity of the AWI for viruses and inlet virus concentration. (C) 2015 Elsevier B.V. All rights reserved.

Fractal dimensions for unsaturated porous media

The analytical expressions of the fractal dimensions for wetting and non-wetting phases for unsaturated porous media are derived and are found to be a function of porosity, maximum and minimum pore sizes as well as saturation. There is no empirical constant in the proposed fractal dimensions. It is also found that the fractal dimensions increase with porosity of a medium and are meaningful only in a certain range of saturation S-w, i.e. S-w > S-min for wetting phase and S-w < S-max for non-wetting phase at a given porosity, based on real porous media for requirements from both fractal theory and experimental observations. The present analysis of the fractal dimensions is verified to be consistent with the existing experimental observations and it makes possible to analyze the transport properties such as permeability, thermal dispersion in unsaturated porous media by fractal theory and technique.

Stereoselective inverse conjugate addition of nitrogen and carbon nucleophiles to allenyl phosphine oxide. Synthesis of α,β-unsaturated phosphine oxides

Issue in Honor of Prof. Paweł Kafarski