Modulation of Reactivities of Dienophiles for DielsAlder Reactions via Complexation of α,β‐Unsaturated Chelating Amides

Abstract

We describe the modulation of reactivities of dienophiles for DielsÀAlder reactions via a new principle based on chelating amides positioned adjacent to their C¼C bond. It is demonstrated for modified acrylic acid derivatives and related dienophiles with three different chelating entities. Complexation of the chelators leads to an intensified electron-withdrawing effect leading to an enhancement of reactivity in DielsÀAlder reactions depending on the complexed metal ion. The application of this new approach might be extended to other reactions with reacting entities adjacent to chelating amides.