Herein is described an efficient and chemoselective method for the synthesis of diversely substituted secondary amines in yields up to 98 %. Direct mono‐ N ‐alkylation of primary benzylamines and anilines with a wide range of alkyl halides is promoted by a cesium base in the absence of any additive or catalyst. The basicity and solubility of cesium carbonate in anhydrous N , N ‐dimethylformamide not only enables mono‐ N ‐alkylation of primary amines but also suppresses undesired dialkylation of the desired amines.
