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(CO2 Et)2 ] and a single C2 -symmetrical bisadduct C70 (CF3 )8 [C(CO2 Et)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(CO2 Et)2 ]H and C70 (CF3 )8 [C(CO2 Et)2 ][CH(CO2 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.
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
Marina G
MG
Apenova
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
Olesya O
OO
Semivrazhskaya
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
Eugenia V
EV
Borkovskaya
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
Nikita M
NM
Belov
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
Ilya N
IN
Ioffe
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
Vitaliy Yu
VY
Markov
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
Sergey I
SI
Troyanov
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia. nso@thermo.chem.msu.ru.
Natalia S
NS
Lukonina
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia.
Lev N
LN
Sidorov
Chemistry Department, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, 119991, Moscow, Russia. aag@thermo.chem.msu.ru.
Alexey A
AA
Goryunkov
density functional calculations; fullerenes; nucleophilic cyclopropanation; reaction mechanism; structure elucidation; trifluoromethyl fullerenes