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Solvent Effects on the 9-Hydroxymethylanthracene + N-Ethylmaleimide Diels−Alder Reaction. A Theoretical Study
journal contribution
posted on 2005-02-18, 00:00 authored by José I. García, José A. Mayoral, Luis SalvatellaThe origin of the high reaction rates of the 9-hydroxymethylanthracene + N-ethylmaleimide Diels−Alder reaction in
fluorous solvents and supercritical carbon dioxide is analyzed through a combination of regression analyses and
theoretical calculations. Both approaches allow the solvent
effects on the activation barrier (a decrease by solvophobic
interactions, an increase by dipolarity−polarizability) to be
attributed to the existence of a hydrogen bond between the
two reactants in the transition state, refuting a previous
hypothesis based on strong solvophobic interactions.