An efficient electrochemical strategy for the deaminative functionalization of alkyl amines has been described. The alkyl bistriflimidates was readily accessed by the treatment of alkyl amines with trifluoromethanesulfonic anhydride and unprecedentedly employed for C−N bond activation. It can be applied to a range of transformations, including borylation, sulfuration, selenation, sulfonation, Additionally, deaminative esterification and amidation can be performed under catalytic base conditions. The protocol features an undivided cell without use of transition metal- or photo-catalysts and exhibits high conversion and stability in flow reactor.