From Internal Olefins to Linear Amines: Ruthenium-Catalyzed Domino Water-Gas Shift/Hydroaminomethylation Sequence

A selective ruthenium-catalyzed water gas shift/hydroformylation of internal olefins and olefin mixtures is reported. This novel domino reaction takes place through a catalytic water-gas shift reaction, subsequent olefin isomerization, followed by hydroformylation and reductive amination. Key to the success for the efficient one-pot process is the use of a specific 2-phosphino-substituted imidazole ligand and triruthenium dodecacarbonyl as precatalyst. Industrially important internal olefins react with various amines to give the corresponding tertiary amines generally in good yield and selectivity This reaction sequence constitutes an economically attractive and environmentally favorable process for the synthesis of linear amines.