An effective base‐induced selective approach for the synthesis of linear and branched N‐alkylated heterocycles by hydroamination of olefins has been described. The designed C–N bond formation method was directed through the olefin, as with styrenes only linear N‐alkylated product was obtained, and acrylates gave linear as well as branched alkylated heterocycles. This protocol provided the synthesis of exclusive N‐alkylated product instead of the C‐3 Michael addition product. The reaction was also compatible with phenyl vinyl sulfone, thus leading to the formation of sulfone substituted heterocycles in good yield. Further, the method was utilized for the synthesis of medicinally important analogs of CB1 Cannabinoid receptor and Dimebon analogue in short reaction sequence.