A panel of natural aliphatic tertiary alkaloids (R3N) were directly converted to R3N+-NH- (without the need to prepare protected aminimides R3N+-NR'(-) followed by deprotection) by [Mn(TDCPP)Cl]catalysed N-amination reaction, with O-(2,4-dinitrophenyl) hydroxylamine as the nitrogen source, in up to 98% yields under mild reaction conditions.