These results point at an important general principle: when an aromatic additive is employed in asymmetric organocatalysis, it can act as a second catalyst by sandwiching itself between the organocatalyst coordinated substrates, and thus serve to improve the enantioselectivity. In otherwords, thecurrentworkwouldenablethe rational design oforganocatalyticsystems. Given the rapid upsurge in interest in organocatalysis in recent years, the insights gained about the role of aromatic additives from the current work can help in the design of more efficient organocatalytic systems in the near future.