Cu-Catalyzed Mild C(sp²)–H Functionalization Assisted by Carboxylic Acids en Route to Hydroxylated Arenes

A formal Cu-catalyzed C­(sp²)–H hydroxylation assisted by benzoic acids is described. The procedure is characterized by its mild reaction conditions and wide substrate scope utilizing simple and cheap Cu catalysts, thus becoming a user-friendly and operationally simple protocol for C­(sp²)–H hydroxylation

Direct Asymmetric Ruthenium-Catalyzed Reductive Amination of Alkyl–Aryl Ketones with Ammonia and Hydrogen

The asymmetric ruthenium-catalyzed reductive amination employing ammonia and hydrogen to primary amines is described. Here we demonstrate the capability of our catalyst to perform a chemo- and enantioselective process while using simple ammonia gas as a reagent, one of the most attractive and industrially relevant nitrogen sources. The presence of a catalytic amount of ammonium iodide was essential for obtaining good yields and enantioselectivities. The mechanism of this reaction was investigated by DFT and we found a viable pathway that also explains the trend and magnitude of enantioselectivity through the halide series in good agreement with the experimental data. The in-depth investigation of substrate conformers during the reaction turned out to be crucial in obtaining an accurate prediction of the enantioselectivity. Furthermore, we report the crystallographic data of the chiral [Ru­(I)­H­(CO)­((<i>S</i>,<i>S</i>)-<i>f</i>-binaphane)­(PPh₃)] complex, which we identified as the most efficient catalyst in our investigation