The (E)-photoenols generated in situ by photolysis of o-tolualdehydes 1-5 in the solid state react with the precursor aldehydes as dienophiles in a hetero-Diels-Alder cycloaddition fashion to afford trans-3-arylisochromanols in excellent yields and in a high diastereoselectivity. An examination of the reactivity of three different classes of rationally designed aldehydes shows that the tandem enolization-Diels-Alder cycloaddition occurs ...
