Nucleophilicity and site selectivity of commonly used arenes and heteroarenes

Abstract

(Figure presented) By using the inverse concept of electrophilicity and nucleophilicity and with four different available equations from literature for electrophilicity and electrodonating power, the nucleophilicity values of 69 commonly used arenes and heteroarenes have been calculated at the B3LYP/6-311+G(d,p) level of theory. The linearity between the nucleophilicity and Hammett ? and ?p values has been chosen as a test to judge the goodness of the methods used. Finally four different arene and heteroarene series (substituted indoles, phenols, pyrroles, and anisoles) have been subjected to local nucleophilicity analysis in order to predict the site selectivity in electrophilic aromatic substitution reactions (EAS). In each case we have obtained excellent correlation with the experimental result. � 2010 American Chemical Society.