Orienting Effect of the Cage Addends: The Case of Nucleophilic Cyclopropanation of C2-C70(CF3)8

C2‐C70(CF3)8 was found to be a very promising substrate in the Bingel and the Bingel–Hirsch reactions combining perfect regioselectivity with much higher reactivity compared to its analogs. The reactions with diethyl malonate yield a single isomer of the monoadduct C70(CF3)8[C(CO2Et)2] and a single C2‐symmetrical bisadduct C70(CF3)8[C(CO2Et)2]2. The Bingel–Hirsch variation is particularly interesting in that it additionally affords, in a similar regioselective manner, the unexpected alkylated derivatives C70(CF3)8[CH(CO2Et)2]H and C70(CF3)8[C(CO2Et)2][CH(CO2Et)2]H. The novel compounds have been isolated and structurally characterized by means of 1H and 19F NMR spectroscopy as well as single‐crystal X‐ray diffraction. The mechanistic and regiochemical aspects of the reaction are explained with the aid of DFT calculations. Conventional vs. unconventional: Acceptor‐derivatized fullerene substrates can exhibit an enhanced reactivity and regioselectivity in important organic reactions. Bingel and Bingel–Hirsch functionalization of C2‐C70(CF3)8 are reported, which affords rapid and LUMO‐directed regioselective formation of both conventional cyclopropanated and unusual alkylated products. The mechanistic and regiochemical aspects of the reaction are explained with the aid of the DFT calculations.