Introduction of alkyl groups on azodicarboxylate esters is an important method to prepare alkyl aminederivatives. Herein, we report reactions of 4-alkyl-1,4-dihydropyridines as alkylation reagents with di-tert-butyl azodicarboxylate to prepare alkyl aminederivatives under heating conditions. The alkylation reactions via C–C bond cleavage of the dihydropyridines are achieved in the absence of catalysts