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.