Anion-π catalysis has been discovered in 2013. The general idea is to stabilize anionic transition states and reactive intermediates on π-acidic surfaces, with anion-π interactions. This idea is completely new. The general objective of the thesis was to secure direct experimental evidence for transition-state recognition on π-acidic surfaces. For this purpose, a series of malonate-bridged naphthalenediimides was synthesized. In these macrocycles, enolate anions are covalently placed on π-acidic aromatic surfaces of systematically varied π acidity. Their presence on the π surface can be seen directly by NMR spectroscopy and X-ray crystallography. A deuterium exchange method was invented to use NMR kinetics to extract enolate-π interactions in intermediates and transition states with maximal credibility but minimal interference. The key results are that anion-π interactions can increase the acidity of enols by a value of up to DpKa = 5.5.