{Reference Type}: Journal Article
{Title}: Orienting Effect of the Cage Addends: The Case of Nucleophilic Cyclopropanation of C2 -C70 (CF3 )8.
{Author}: Apenova MG;Semivrazhskaya OO;Borkovskaya EV;Belov NM;Ioffe IN;Markov VY;Troyanov SI;Lukonina NS;Sidorov LN;Goryunkov AA;
{Journal}: Chem Asian J
{Volume}: 10
{Issue}: 6
{Year}: Jun 2015
{Factor}: 4.839
{DOI}: 10.1002/asia.201500079
{Abstract}: 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.