Selectivity in the electron transfer catalyzed Diels-Alder reaction of (R)-alpha-phellandrene and 4-methoxystyrene

Abstract

Electron transfer catalysis is an effective method for the acceleration of Diels-Alder reactions between two substrates of similar electron density. The dependence of the selectivity of the Diels-Alder reaction between (R)-alpha-phellandrene and 4-methoxystyrene catalyzed by photoinduced electron transfer with tris(4-methoxyphenyl) pyrylium tetrafluoroborate is studied. Despite the fact that the radical ions involved are highly reactive species, complete regioselectivity favoring attack on the more highly substituted double bond is observed. The endo/exo selectivity and the periselectivity between [4 + 2] and [2 + 2] cycloaddition is found to be solvent-dependent. Stereochemical analysis showed that the periselectivity is correlated with the facial selectivity, with attack trans to the isopropyl group leading to the [4 + 2] product and cis attack leading to the formation of the [2 + 2] product. A good correlation between the dielectric constant of the solvent and the endo/ exo ratio is found, but more polar solvents lead to lower periselectivity. The effect of reactant and catalyst concentrations is found to be smaller. These results are rationalized in the context of the relative stability of the ion-molecule complexes and the singly linked intermediate of the reaction.