Highly Regioselective Carbonylation of Unactivated C(sp³)–H Bonds by Ruthenium Carbonyl

The regioselective carbonylation of unactivated C(sp3)–H bonds of aliphatic amides was achieved using Ru3(CO)12 as a catalyst. The presence of a 2-pyridinylmethylamine moiety in the amide is crucial for a successful reaction. The reaction shows a preference for C–H bonds of methyl groups as opposed to methylene C–H bonds and tolerates a variety of functional groups. The stoichiometric reaction of an amide with Ru3(CO)12 gave a dinuclear ruthenium complex in which the 2-pyridinylmethylamino moiety was coordinated to the ruthenium center in an N,N manner.