Theoretical reactivity indices based on the conceptual Density Functional Theory (DFT) have become a powerful tool for the semiquantitative study of organic reactivity. A large number of reactivity indices have been proposed in the literature. Herein, global quantities like the electronic chemical potential μ, the electrophilicity ω and the nucleophilicity N indices, and local condensed indices...

The Front Cover illustrates the ability of DBU – yellow tightrope walker to preserve fluoride nucleophilicity promoting fluorination a pentafluoroisobutenyl group five-flower bouquet carried by young lady in cascade reaction. In contrast, alkali metals blue acrobats precipitate with ions precluding subsequent hydrofluorination. created Ludion. More information can be found Research Article G. G...

Abstract We review the early works which were precursors of Conceptual Density Functional Theory. Starting from Thomas–Fermi approximation and exact formulation Theory by Hohenberg Kohn’s theorem, we will introduce electronegativity theory hard soft acids bases. also present a general introduction to Fukui functions, their relation with nucleophilicity electrophilicity, an emphasis towards impo...

In a previous work (L. R. Domingo, M. J. Aurell, P. Perez and R. Contreras, Tetrahedron 2002, 58, 4417) we proposed that the difference in global electrophilicity index be taken as a measure of the polarity at the transition state in intermolecular Diels-Alder reactions. We herein extend this model to deal with intramolecular Diels-Alder (IMDA) processes. The transferability of the empirical re...

A challenge in the computational design of enzymes is that multiple properties, including substrate binding, transition state stabilization and product release, must be simultaneously optimized, and this has limited the absolute activity of successful designs. Here, we focus on a single critical property of many enzymes: the nucleophilicity of an active site residue that initiates catalysis. We...

A theoretical study of a series of five glucose based glycolipid crown ethers and their complexes with Na(+) and K(+) was performed using the density functional theory with B3LYP/6-31 G* to obtain the optimized geometrical structures and electronic properties. The local nucleophilicity of the five molecules was investigated using Fukui function, while the global nucleophilicity was calculated f...

the effects of halogens; fluorine, chlorine and bromine, on the stability and multiplicity of phenylcarbenes / silylenes/ germylenes structures are compared and contrasted at b3lyp/6-311++g**//b3lyp/6-31+g* level. the singlet-triplet energy gaps, δes-t , values for all the above speciesincrease through fluorinated up, δes-ts and δehomo–lumos support the stability of the singlet statesinspite of...

In spite of the enormous importance, reactions of cationic electrophiles with silylated enol ethers have adopted in organic synthesis,* kinetic data on such reactions are rare.u Previously we have reported rate constants for the reactions of alkenes, allylelement compounds, and enol ethers toward chloro-, methyl-, and alkoxy-substituted benxhydryl cation& Because of the high nucleophilicity of ...