A novel, one-pot reductive mono-alkylation method of amines (primary and secondary), 1,2-phenylenediamine, O-trimethylsilyl-hydroxylamine, and N,N-dimethylhydrazine was developed using LiClO4 (5 mol %) as a source for in situ generation of imine, iminium ion, oxime, and hydrazone, and zirconium borohydride-piperazine complex as reducing agent. This condition is especially useful for situations in which it is not practical to use the amine in excess (as is typically the case under acid-catalyzed conditions) or for acid-sensitive compounds. (c) 2007 Elsevier Ltd. All rights reserved.