Elucidation of the atroposelectivity in the synthesis of axially chiral thiohydantoin derivatives.

Recently, Sarigul and Dogan have synthesized a number of enantiomerically enriched axially chiral atropoisomeric 2-thiohydantoins by the reaction of l-amino acid ester salts and o-aryl isothiocyanates in the presence of triethyl amine (TEA) in dichloromethane. The non-axially chiral derivative 5-methyl-3-phenyl-2-thiohydantoin gave a racemic product whereas the axially chiral 5-methyl-3-o-bromophenyl-2-thiohydantoin was less prone to racemize at C5 of the heterocyclic ring. In this study, we present a computational study (M06-2X/6-311+G(d,p) for C, H, O, N and S; M06-2X/6-311++G(3df,3pd) for Br) in order to propose plausible mechanisms for the racemization and cyclization steps for 2-thiohydantoin derivatives.

Hydroxyl radical-mediated degradation of salicylic acid and methyl paraben: an experimental and computational approach to assess the reaction mechanisms.

Advanced oxidation processes (AOPs) using various energy sources and oxidants to produce reactive oxygen species are widely used for the destruction of recalcitrant water contaminants. The current study is about the degradation of two emerging pollutants-salicylic acid (SA) and methyl paraben (MP)-by high-frequency ultrasonication followed by identification of the oxidation byproducts and modeling of the reaction mechanisms using the density functional theory (DFT). The study also encompasses prediction of the aquatic toxicity and potential risk of the identified byproducts to some aquatic organisms bussing the ECOSAR (Ecological Structure Activity Relationships) protocol.

Stimuli-responsive poly(hydroxyethyl methacrylate) hydrogels from carboxylic acid-functionalized crosslinkers.

Tailoring hydrogel properties by modifications of the crosslinker structure is a good method for the design of hydrogels with a wide range of properties. In this study, two novel carboxylic acid-functionalized dimethacrylate crosslinkers (1a and 2a) are synthesized by the reaction of poly(ethylene glycol) or 2-hydroxyethyl disulfide with tert-butyl α-bromomethacrylate followed by cleavage of tert-butyl groups using trifluoroacetic acid. Their copolymerization reactivity with 2-hydroxyethyl methacrylate (HEMA) investigated by photopolymerization studies performed on photo-differential scanning calorimetry shows higher reactivity of 2a compared to 1a.

Role of ionic liquids on the selectivity and the rate of organic reactions: A computational approach.

In the last years, ionic liquids have been used as substitutes to common solvents since they combine good solubility properties with small vapor pressures. Herein, the Diels-Alder reactions of cyclopentadiene (CP) with acrolein, methyl acrylate and acrylonitrile in ionic liquids ([Emim][N(Tf)]), ([Hbim][N(Tf)]) and ([Bmim][OTf]) have been modeled with density functional theory to explore the effect of ionic liquids on the endo selectivity in the adducts. Besides the hydogen bonding interactions between the cation and the diene in all the structures, endo transition structures are slightly better stabilized than exo transition structures because of the favorable interactions between the H's of the CP ring and the O's of the [N(Tf)] and [OTf] anions of the IL's.

Hydroxyl radical-mediated degradation of diclofenac revisited: a computational approach to assessment of reaction mechanisms and by-products.

Advanced oxidation processes (AOPs) are based on the in situ production of hydroxyl radicals (•OH) and reactive oxygen species (ROS) in water upon irradiation of the sample by UV light, ultrasound, electromagnetic radiation, and/or the addition of ozone or a semiconductor. Diclofenac (DCF), one of the emerging organic contaminants (EOC), is of environmental concern due to its abundancy in water and is known to be subjected to AOPs. The current study uses density functional theory (DFT) to elucidate the mechanisms of the reactions between •OH and DCF leading to degradation by-products, P1-P9.

1,3-Dipolar Cycloaddition Reactions of Low-Valent Rhodium and Iridium Complexes with Arylnitrile N-Oxides.

The reactions between low-valent Rh(I) and Ir(I) metal-carbonyl complexes and arylnitrile oxides possess the electronic and structural features of 1,3-dipolar cycloadditions. Density functional theory (DFT) calculations on these reactions, involving both cyclopentadienyl and carboranyl ligands on the metal carbonyl, explain the ease of the chemical processes and the stabilities of the resulting metallaisoxazolin-5-ones. The metal-carbonyl bond has partial double bond character according to the Wiberg index calculated through NBO analysis, and so the reaction can be considered a normal 1,3-dipolar cycloaddition involving M═C bonds.

The origin of exo-stereoselectivity of norbornene in hetero Diels-Alder reactions.

In this study the exo selectivity in the hetero Diels-Alder reaction of atropisomeric 5-benzylidine-2-arylimino-3-aryl-thiazolidine-4-thiones with norbornene was investigated with computational tools. Taking into account the M/P chiral character of the o-methoxyphenyl substituted heterodienes in addition to the exo/endo selectivity, 8 different transition structures were located. Based on the direction of approach of the diene and the dienophile for each plausible path it is found that endo products are not preferred because of the large distortion of norbornene and the rather eclipsed conformations of these transition state structures.