Hierarchical Selectivity in Fullerenes: Site‐, Regio‐, Diastereo‐, and Enantiocontrol of the 1,3‐Dipolar Cycloaddition to C70

Make your choice of stereochemistry: The first enantioselective cycloaddition of N-metalated azomethine ylides to the C70 molecule affords both pyrrolidino[70]fullerene enantiomers, with ee values over 90 %, depending on the chiral metal complex used (see picture). The high site- and regioselectivity observed has been accounted for by the nucleophilic and electrophilic Fukui indexes determined by theoretical calculations.