Ru‐Catalyzed Deoxygenative Transfer Hydrogenation of Amides to Amines with Formic Acid/Triethylamine

A ruthenium(II)‐catalyzed deoxygenative transfer hydrogenation of amides to amines using HCO 2 H/NEt 3 as the reducing agent is reported for the first time. The catalyst system consisting of [Ru(2‐methylallyl) 2 (COD)], 1,1,1‐tris(diphenylphosphinomethyl) ethane (triphos) and Bis(trifluoromethane sulfonimide) (HNTf 2 ) performed well for deoxygenative reduction of various secondary and tertiary amides into the corresponding amines in high yields with excellent selectivities, and exhibits high tolerance toward functional groups including those that are reduction‐sensitive. The choice of hydrogen source and acid co‐catalyst is critical for catalysis. Mechanistic studies suggest that the reductive amination of the in situ generated alcohol and amine via borrowing hydrogen is the dominant pathway. magnified image