Understanding the mechanisms of [3+2] cycloaddition reactions. The pseudoradical versus the zwitterionic mechanism |
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Authors: | Luis R Domingo Saeed R Emamian |
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Institution: | 1. Departamento de Química Orgánica, Universidad de Valencia, Dr. Moliner 50, E-46100 Burjassot, Valencia, Spain;2. Chemistry Department, Shahrood Branch, Islamic Azad University, Shahrood, Iran |
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Abstract: | Analysis of 12 three-atom-components (TACs) participating in 3+2] cycloaddition (32CA) reactions towards ethylene and acetylene allows establishing good correlations between the pseudodiradical character, the hardness η, and the nucleophilicity N index of the TAC with the feasibility of these non-polar reaction. These results allow the introduction of the pr index, which comprises the two aforementioned DFT reactivity indices. The increase of the pr index for an allylic-type TAC goes accompanied by a linear decrease of the activation enthalpy of the reaction. The present study makes it possible to establish a useful classification of 32CA reactions into zw-type reactions involving TACs with a high zwitterionic character, and pr-type reactions involving TACs with a high pseudodiradical character. |
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