Two different products were obtained by the regiodivergent
reaction
of benzoquinone derivatives with phenolates and anilines: 3-aryloxybenzoquinone
and 2-phenylamino-3-bromobenzoquinone. Calculated density functional
theory free energies of reaction values corroborate the experimental
observation of the formation of the substitution product in the reaction
with phenolates in acetonitrile and the product of addition/oxidation
for the reaction with aniline in water. Calculated charges and Fukui
functions are similar for C2 and C3 atoms, indicating an equal possibility
to suffer a nucleophilic attack. The calculated energy barriers for
nucleophilic attack steps indicated that the first steps of the substitution
with phenolates and addition/oxidation with anilines are faster, which
justifies the formation of the respective products. The natural bond
order analysis for the transition states revealed that there is a
strong interaction between lone pairs of N and O atoms and the πC2C3
* for the O →
C2 and N → C3 attacks and a weak interaction for the O →
C3 and N → C2 attacks, which also agrees with experimental
observations.
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