Orienting Effect of the Cage Addends: The Case of Nucleophilic Cyclopropanation of C 2 ‐C 70 (CF 3 ) 8

C 2 ‐C 70 (CF 3 ) 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 C 70 (CF 3 ) 8 [C(CO 2 Et) 2 ] and a single C 2 ‐symmetrical bisadduct C 70 (CF 3 ) 8 [C(CO 2 Et) 2 ] 2 . The Bingel–Hirsch variation is particularly interesting in that it additionally affords, in a similar regioselective manner, the unexpected alkylated derivatives C 70 (CF 3 ) 8 [CH(CO 2 Et) 2 ]H and C 70 (CF 3 ) 8 [C(CO 2 Et) 2 ][CH(CO 2 Et) 2 ]H. The novel compounds have been isolated and structurally characterized by means of 1 H and 19 F 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.