Energy Decomposition Analysis Reveals the Nature of Lone Pair−π Interactions with Cationic π Systems in Catalytic Acyl Transfer Reactions

Lone pair−π (LP−π) interactions between Lewis basic heteroatoms, such as oxygen and sulfur, and electron-deficient π systems are important noncovalent interactions. However, they have seldom been used to control catalyst–substrate interactions in catalysis. We performed density functional theory calculations to investigate the strengths of LP−π interactions between different lone pair donors and cationic π systems, and in different complexation geometries. Energy decomposition analysis calculations indicated that the dominant stabilizing force in LP−π complexes is electrostatic interaction and the electrostatic potential surface of the π system predicts the most favorable site for forming LP−π complexes. Benzotetramisole (BTM) is revealed as a privileged acyl transfer catalyst that promotes LP−π interactions because the positive charge of the acylated BTM is delocalized onto the dihydroimidazole ring, which binds strongly with a variety of oxygen and sulfur lone pair donors.