title: DFT-HSAB prediction of regioselectivity in 1,3-dipolar cycloadditions: behavior of (4-substituted)benzonitrile oxides towards methyl propiolate.
abstract: 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.
authors.affiliation: Consiglio Nazionale delle Ricerche, Istituto di Scienze e Tecnologie Molecolari via Golgi 19, 20133 Milano, Italy. alessandro.ponti@istm.cnr.it
authors.forename: Alessandro
authors.initials: A
authors.lastname: Ponti
authors.forename: Giorgio
authors.initials: G
authors.lastname: Molteni