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In this case we could not detect any signals corresponding to dehy-
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In this work we have investigated the oxidative coupling
of resveratrol induced by copper and iron ions. The formation
of racemic ␦-viniferin dehydrodimer 3 is observed in ESI-MS
experiments carried out on resveratrol-copper mixtures, while
the analogous resveratrol-iron reaction affords the racemic -
viniferin dehydrodimer 4. Computational results suggest that
dehydrodimers 3 and 4 are formed by coupling reactions, and sub-
sequent intramolecular nucleophilic attack, of phenoxide radicals.
The latter are produced in the oxidation reaction of phenoxide
anions by Cu(II) and Fe(III) ions. We find that Cu(II) preferentially
produces the 4ꢀ-O resveratrol radical An, while Fe(III) produces
more easily the 3-O resveratrol radical Bn. Given that the forma-
tion of dehydrodimer 3 requires An radicals as reactants, whereas
that of dehydrodimer 4 also needs Bn radicals, these computational
findings explain why reactions of resveratrol with Cu and Fe ions
eventually result in the production of species 3 and 4, respectively.
Calculated enthalpies in gas phase and in water solution for the
reaction paths leading to the two isomeric dehydrodimers sug-
gest that the ESI-MS approach is an adequate technique to study
the resveratrol reactivity in solution. In addition, we have inves-
tigated the structure-reactivity relationship by studying synthetic
analogues of resveratrol. We find that the presence of the OH group
in para position is crucial for the reactivity and biological behavior
of resveratrol.
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