As the result of the Thesis, several methods based on intramolecular amination of nonclassical cyclopropylmethyl cation for synthesis of homoallylamine, 1-amino-1-cyclobutylcarbinol and 1-amino-1-cyclobutane carboxylic acid derivatives were developed. Synthesis of cyclopropyl-containing heterocycles from 1,2-disubstituted cyclopropanes was demonstrated based on selective cyclopropyl-cyclopropyl rearrangement. Regioselective protonolysis of cyclopropane C-C bond using protonated amide as internal proton donor was developed. Directing groups such as carbamate, carboxamide, urea, ester and ketone were found efficient for regioselective anti-Markovnikov cleavage of cyclopropane. An intramolecular and an intermolecular amination of carbenium ions generated by directed regioselective protonolysis of cyclopropane were demonstrated.