We report a nickel(0)-catalyzed direct transfer hydrogenation (TH) of a variety of alkyl–aryl, diaryl, and aliphatic ketones with ethanol. This protocol implies a reaction in which a primary alcohol serves as a hydrogen atom source and solvent in a one-pot reaction without any added base. The catalytic activity of the nickel complex [(dcype)Ni(COD)] (e) (dcype: 1,2-bis(dicyclohexyl-phosphine)ethane, COD: 1,5-cyclooctadiene), towards transfer hydrogenation (TH) of carbonyl compounds using ethanol as the hydrogen donor was assessed using a broad scope of ketones, giving excellent results (up to 99% yield) compared to other homogeneous phosphine–nickel catalysts. Control experiments and a mercury poisoning experiment support a homogeneous catalytic system; the yield of the secondary alcohols formed in the TH reaction was monitored by gas chromatography (GC) and NMR spectroscopy.

In recent years, many manganese-based homogeneous catalytic precursors have been developed as powerful alternatives in organic synthesis. Among these, the hydrofunctionalizations of unsaturated C-C bonds correspond to outstanding ways to afford compounds with more versatile functional groups, which are commonly used as building blocks in the production of fine chemicals and feedstock for the industrial field. Herein, we present an account of the Mn-catalyzed homogeneous hydrofunctionalizations of alkenes and alkynes with the main objective of finding catalytic and mechanistic tendencies that could serve as a platform for the works to come.