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)((S,S)-f-binaphane)(PPh3)] complex, which we identified as the most efficient catalyst in our investigation.

Mild ArI-catalyzed C(sp²)-H or C(sp³)-H functionalization/C-O formation: an intriguing catalyst-controlled selectivity switch.

A tandem C(sp(2))-H and C(sp(3))-H functionalization/C-O bond formation catalyzed by iodine(III) reagents generated in situ has been developed. The method shows wide scope under mild conditions and exhibits an unprecedented selectivity profile that can be switched depending on the catalyst employed.

Cu-catalyzed mild C(sp2)-H functionalization assisted by carboxylic acids en route to hydroxylated arenes.

A formal Cu-catalyzed C(sp(2))-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(sp(2))-H hydroxylation.