Hydrosilylative reduction of primary amides to primary amines catalyzed by a terminal [Ni-OH] complex.

A terminal [Ni-OH] complex 1, supported by triflamide-functionalized NHC ligands, catalyzes the hydrosilylative reduction of a range of primary amides into primary amines in good to excellent yields under base-free conditions with key functional group tolerance. Catalyst 1 is also effective for the reduction of a variety of tertiary and secondary amides. In contrast to literature reports, the reactivity of 1 towards amide reduction follows an inverse trend, i.e., 1° amide > 3° amide > 2° amide. The reaction does not follow a usual dehydration pathway.