Conversion of 2-unsubstituted pyridines to 2-aminopyridines could be achieved via a simple oxidation to pyridine N-oxides followed by a general and efficient amination using TsO₂/t-BuNH₂ and then in situ deprotection with TFA. The amination proceeded in high yields, excellent 2-/4-selectivity and good functional group compatibility. 2-Amino (iso)quinolines were also obtained in the same manner. One pot of 2-amination followed by  TFA deprotection could be easily scaled up to multi-kilograms.