The intermolecular aminative difunctionalization of alkenes with electron-rich amino sources represents a streamlined access to alkylamines of high value in medicinal and material chemistry. The prevailing methods involve migratory insertion of olefin followed by an electrophilic amination of the resulting C(sp3)-M species. However, this ionic strategy is limited to aminoboration and carboamination reactions. Recent advances have demonstrated that utilization of alkyl aminyl radicals offers a promising approach to alkene difunctionalization.