During 1,3 dipolar reactions of unsymmetrical mesoionic Münchnones (1) to substituted nitrostyrenes (2), bicyclic intermediates (3) are formed, which then decompose to two observed products (4, 5), the ratio of which is contrary to expected ratios based on known electrostatics. Earlier computational studies revealed a secondary transition state in one of the reaction paths, which provided a plausible explanation for the observed product ratio. An additional, more detailed computational study, utilizing Hartree-Fock calculations with Møller-Plesset energy correlation corrections (MP2), was undertaken to validate activation energies that are more consistent with experimental product ratios.

Computational study of activation energies in 1,3-dipolar cycloadditions

249th National Meeting (2015)

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