The Effect of Conformational Freedom vs Restriction on the Rate in Asymmetric Hydrogenation: Iridium-Catalyzed Regio- and Enantioselective Monohydrogenation of Dienones.

Transition metal-catalyzed asymmetric hydrogenation constitutes an efficient strategy for the preparation of chiral molecules. When dienes are subjected to hydrogenation, control over regioselectivity still presents a large challenge and the fully saturated alkane is often yielded. A few successful monohydrogenations of dienes have been reported, but hitherto these are only efficient for dienes comprised of two distinctly different olefins.

Rational selection of co-catalysts for the deaminative hydrogenation of amides.

The catalytic hydrogenation of amides is an atom economical method to synthesize amines. Previously, it was serendipitously discovered that the combination of a secondary amide co-catalyst with (PNP)Fe(H)(CO) (PNP = N[CHCH(PPr)] ), results in a highly active base metal system for deaminative amide hydrogenation. Here, we use DFT to develop an improved co-catalyst for amide hydrogenation.

Highly selective hydrogenation of amides catalysed by a molybdenum pincer complex: scope and mechanism.

A series of molybdenum pincer complexes has been shown for the first time to be active in the catalytic hydrogenation of amides. Among the tested catalysts, proved to be particularly well suited for the selective C-N hydrogenolysis of -methylated formanilides. Notably, high chemoselectivity was observed in the presence of certain reducible groups including even other amides.