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Arylazide Cycloaddition to Methyl Propiolate: DFT‐Based Quantitative Prediction of Regioselectivity
Author(s) -
Molteni Giorgio,
Ponti Alessandro
Publication year - 2003
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200204681
Subject(s) - regioselectivity , hsab theory , cycloaddition , carbon tetrachloride , chemistry , computational chemistry , density functional theory , reactivity (psychology) , molecular orbital , solvent effects , solvent , molecule , organic chemistry , catalysis , medicine , alternative medicine , pathology
Several 1(4‐substituted)phenyl‐4‐ or 5methoxycarbonyl‐1,2,3‐triazoles have been synthesized by 1,3‐dipolar cycloaddition of the corresponding arylazides to methyl propiolate in carbon tetrachloride. The regioselectivity of these reactions cannot be rationalized on the basis of the electronic demands of the reactants or frontier molecular‐orbital theory. Therefore, we applied to this problem a quantitative formulation of the HSAB principle to this problem developed within density functional theory. Global and local reactivity indices were computed at B3LYP/6‐311+G(d,p) level both in vacuo and in carbon tetrachloride (by the COSMO approach). The direction of charge transfer upon reactive encounter has been determined and the computed regioselectivity has been shown to be in good agreement with the experimental results. The relationship between computed and experimental data and how it is affected by the solvent have been discussed.