The energetics of tetrahydrocarbazole aromatization over Pd(111): A computational analysis

The carbazole moiety is a component of many important pharmaceuticals including anticancer and anti-HIV agents and is commonly utilized in the production of modern polymeric materials with novel photophysical and electronic properties. Simple carbazoles are generally produced via the aromatization of the respective tetrahydrocarbazole (THCZ). In this work, density functional theory calculations are used to model the reaction pathway of tetrahydrocarbazole aromatization over Pd(111). The geometry of each of the intermediate surface species has been determined and how each structure interacts with the metal surface addressed. The reaction energies and barriers of each of the elementary surface reactions have also been calculated, and a detailed analysis of the energetic trends performed. Our calculations have shown that the surface intermediates remain fixed to the surface via the aromatic ring in a manner similar to that of THCZ. Moreover, the aliphatic ring becomes progressively more planer with the dissociation of each subsequent hydrogen atom. Analysis of the reaction energy profile has revealed that the trend in reaction barriers is determined by the two factors: (i) the strength of the dissociating ring-H bond and (ii) the subsequent gain in energy due to the geometric relaxation of the aliphatic ring. (c) 2008 American Institute of Physics.

Supported and liquid phase task specific ionic liquids for base catalysed Knoevenagel reactions

A series of Hunig's base tethered ammonium ionic liquids have been used to catalyse the Knoevenagel condensation of aldehydes/ketones with malononitrile and ethyl cyanoacetate. The reactions were performed under homogeneous and under biphasic, liquid-liquid and liquid-silica supported ionic liquid, conditions with the biphasic systems employing cyclohexene as the second phase. By increasing the distance between the ammonium head group and Hunig's base the activity of the catalyst was found to increase. Higher activity, in general, was found under homogeneous reaction conditions; however, the recyclability of the catalyst was improved by supporting the BIL under biphasic conditions. (c) 2007 Elsevier B.V. All rights reserved.

Recyclable copper catalysts based on imidazolium-tagged bis(oxazolines): A marked enhancement in rate and enantioselectivity for Diels-Alder reactions in ionic liquid

Imidazolium-tagged bis(oxazolines) have been prepared and used as chiral ligands in the copper(II)-catalysed Diels-Alder reaction of N-acryloyl- and N-crotonoyloxazolidinones with cyclopentadiene and 1,3-cyclohexadiene in the ionic liquid 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [emim][NTf2]. A significant and substantial enhancement in the rate and enantioselectivity was achieved in [emim][NTf2] compared with dichloromethane. For example, complete conversion and enantioselectivities up to 95 % were obtained for the reaction between N-acryloyloxazolidinone and cyclopentadiene within 2 min in [emim][NTf2] whereas the corresponding reaction in dichloromethane required 60 min to reach completion and gave an ee of only 16 %. The enhanced rates obtained in the ionic liquid enabled a catalyst loading as low as 0.5 mol % to give complete conversion within 2 min while retaining the same level of enantioselectivity. The imidazolium-tagged catalysts can be recycled ten times without any loss in activity or enantioselectivity and showed much higher affinity for the ionic liquid phase during the recycle procedure than the analogous uncharged ligand.

Stabilization of Ti-molecular sieve catalysts used in selective sulfoxidation reactions by ionic liquids

Sulfoxidation reactions of 4,6-dimethyl-2-methylthiopyrimidine have been performed using titanosilicate catalysts in ionic liquids, dioxane and ethanol. The ionic liquid reactions showed superior reactivity compared with molecular solvents. Moreover, on examination of the recycling of the catalyst, a significant increase in the stability of catalyst was found both in terms of recycling activity and leaching of the titanium from the catalyst. The mechanism by which the ionic liquid reduces the solubilisation of the catalysts is explored.

Marked enantioselectivity enhancements for Diels-Alder reactions in ionic liquids catalysed by platinum diphosphine complexes

Asymmetric Diels-Alder reactions using platinum complexes of BINAP, or of conformationally flexible NUPHOS-type diphosphines, have been compared in dichloromethane and selected ionic liquids. Significant enhancements in the enantioselectivity (Deltaee approximate to 20%), as well as reaction rate, were achieved in ionic liquids compared with the organic media.