The Regioselectivity of Bingel-Hirsch Cycloadditions on Isolated Pentagon Rule Endohedral Metallofullerenes

In this work, the Bingel–Hirsch addition of diethylbromomalonate to all non‐equivalent bonds of Sc3N@D3h‐C78 was studied using density functional theory calculations. The regioselectivities observed computationally allowed the proposal of a set of rules, the predictive aromaticity criteria (PAC), to identify the most reactive bonds of a given endohedral metallofullerene based on a simple evaluation of the cage structure. The predictions based on the PAC are fully confirmed by both the computational and experimental exploration of the Bingel–Hirsch reaction of Sc3N@D5h‐C80, thus indicating that these rules are rather general and applicable to other isolated pentagon rule endohedral metallofullerenes. The Bingel–Hirsch (BH) addition of diethylbromomalonate to all non‐equivalent bonds of Sc3N@D3h‐C78 was studied using DFT calculations. A set of rules, the predictive aromaticity criteria (PAC), is proposed to identify the most reactive bonds of endohedral metallofullerenes. The PAC predictions are consistent with computational and experimental data, indicating their generality.