1, 3-dipolar cycloaddition of C-phenyl carbamoyl-N-phenyl nitrone with some dialkyl-substituted 2-benzylidenecyclopropane-1,1-dicarboxylates: theoretical analysis of mechanism and regioselectivity

The regiochemistry of 1,3-dipolar cycloaddition reactions of C-phenyl carbamoyl-N-phenyl nitrone with some dialkyl-substituted 2-benzylidenecyclopropane-1,1-dicarboxylates as dipolarophile was investigated using density functional theory-based reactivity indexes and activation energy calculations at B3LYP/6-31G(d) level of theory. Analysis of the geometries and bond orders at the TS structures associated with the different reaction pathways shows that these 1,3-dipolar cycloaddition reactions occur via an asynchronous concerted mechanism. Analysis of the local electrophilicity and nucleophilicity indexes based on Parr functions only for reaction between 1 + 2a and based on Fukui functions only for 1 + 2b gives correct regioselectivity. The theoretical results obtained in the work clearly predict the regiochemistry of the isolated cycloadducts and agree to experimental results.