Chemoselective Hydrogenation of Carbonyl Compounds and Acceptorless Dehydrogenative Coupling of Alcohols

OsHCl(CO)[κ3-PyCH2NHC2H4NHPtBu2] is the first efficient catalyst for chemoselective reduction of challenging unsaturated esters to enols and for acceptorless coupling of amines with MeOH and EtOH affording formamides and acetamides. The NMR, ESI-MS, and DFT data indicate a mechanism proceeding in the metal coordination sphere and producing no free organic intermediates.