2-Substituted 1,4-Naphthoquinones in [6 + 4]-Cycloaddition with 8,8-Dicyanoheptafulvene

This study demonstrates that classical lowest unoccupied molecular orbital reactivity of 2-substituted 1,4-naphthoquinones is possible to be reversed by deprotonation and application of the resulting dienolate as a 4π component in the higher-order [6 + 4]-cycloaddition proceeding in a completely pericyclic manner. 8,8-Dicyanoheptafulvene was shown to be an efficient 6π component in the developed reaction opening the access to functionalized cycloadducts in a diastereoselective manner by employing organocatalytic activation. Attempts to introduce enantioselective version of the developed higher-order cycloaddition were also undertaken.