This study demonstrates the use of organocatalytic Brønsted base activation of 5-substituted-furan-2(3H)-ones to generate 2π-components for the diastereoselective [8 + 2]-cycloaddition involving 8,8-dicyanoheptafulvene as an 8π-component. The use of dienolates in a higher-order cycloaddition reaction leads to the formation of biologically relevant polycyclic products bearing a γ-butyrolactone structural motif, thus broadening the synthetic potential of Brønsted base activated higher-order cycloadditions.