Premium
DFT‐HSAB Prediction of Regioselectivity in 1,3‐Dipolar Cycloadditions: Behavior of (4‐Substituted)benzonitrile Oxides towards Methyl Propiolate
Author(s) -
Ponti Alessandro,
Molteni Giorgio
Publication year - 2006
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.200500739
Subject(s) - hsab theory , regioselectivity , benzonitrile , chemistry , density functional theory , computational chemistry , reactivity (psychology) , molecular orbital , medicinal chemistry , organic chemistry , molecule , medicine , alternative medicine , pathology , catalysis
The regioselectivity of 1,3‐dipolar cycloadditions between (4‐substituted)benzonitrile oxides and methyl propiolate cannot be rationalized on the basis of the electron demand of the reactants or frontier molecular‐orbital theory. To this problem, we have applied a quantitative formulation of the hard–soft acid–base principle developed within the density functional theory. Global and local reactivity indices were computed at B3LYP/6‐311+G(d,p) level. The details of charge transfer upon the reactive encounter have been elucidated, and the computed regioselectivity has been shown to be in good agreement with experimental data.