Ruthenium‐Catalyzed Synthesis of Secondary Alkylamines: Selective Alkylation with Aliphatic Amines

The chemoselective N‐alkylation of tert‐alkylamines applying aliphatic amines is described for the first time. In the presence of the Shvo catalyst 1, tert‐octylamine 4 and 1‐adamantylamine 5 are alkylated using primary, secondary, and even tertiary amines to give the corresponding monoalkylated tert‐alkylamine in moderate to very good yields and excellent selectivity. This novel reaction proceeds without an additional hydrogen source and ammonia is formed as the only by‐product.