Phosphine- and Hydrogen-Free: Highly Regioselective Ruthenium-Catalyzed Hydroaminomethylation of Olefins

A highly regioselective ruthenium-catalyzed hydroaminomethylation of olefins is reported. Using easily available trirutheniumdodecacarbonyl an efficient sequence consisting of a water-gas shift reaction, hydroformylation of olefins, with subsequent imine or enamine formation and final reduction is realized. This novel procedure is highly practical (ligand-free, one pot) and economic (low catalyst loading and inexpensive metal). Bulk industrial as well as functionalized olefins react with various amines to give the corresponding tertiary amines generally in high yields (up to 92%), excellent regioselectivities (n/iso > 99:1), and full chemoselectivity in favor of terminal olefins.