Mild N‐Alkylation of Amines with Alcohols Catalyzed by the Acetate Ru(OAc) 2 (CO)(D i PPF) Complex

The acetate complex Ru(OAc) 2 (D i PPF) ( 2 ) obtained from Ru(OAc) 2 (PPh 3 ) 2  ( 1 ) and 1,1′‐bis(diisopropylphosphino)ferrocene (D i PPF) reacts cleanly with formaldehyde affording Ru(OAc) 2 (CO)(D i PPF) ( 3 ) in high yield. The monocarbonyl complex  3 (0.4‐2 mol %) efficiently catalyzes the N‐alkylation of primary and secondary alkyl and aromatic amines using primary alcohols ROH (R=Et, n Pr, n Bu, PhCH 2 ) under mild reaction conditions (30–100 °C) with an alcohol/amine molar ratio of 10‐100. Formation of the monohydride RuH(OAc)(CO)(D i PPF) ( 4 ) has been observed by reaction of 3 with i PrOH in the presence of NEt 3 at RT through an equilibrium reaction.