Quantifying the Role of Anion-π Interactions in Anion-π Catalysis

Matile et al. introduced the concept of anion-pi catalysis [Angew. Chem., Int. Ed. 2013, 52, 9940; J. Am. Chem. Soc. 2014, 136, 2101], reporting naphthalene diimide (NDI)-based organocatalysts for the Kemp elimination reaction. We report computational analyses of the operative noncovalent interactions, revealing that anion-pi interactions actually increase the activation barriers for some of these catalyzed reactions. We propose new catalysts that are predicted to achieve significant lowering of the activation energy through anion-pi interactions.