Site-Selective Copper(I)-Catalyzed Hydrogenation of Amides.

We present a bifunctional catalyst consisting of a copper(I)/N-heterocyclic carbene and an organocatalytic guanidine moiety that enables, for the first time, a copper(I)-catalyzed reduction of amides with H as the terminal reducing agent. The guanidine allows for reactivity tuning of the originally weakly nucleophilic copper(I) hydrides - formed in situ - to be able to react with difficult-to-reduce amides. Additionally, the guanidine moiety is key for the selective recognition of "privileged" amides based on simple and readily available heterocycles in the presence of other amides within one molecule, giving rise to hitherto unknown site-selective catalytic amide hydrogenation.

Mechanochemical solid state synthesis of copper(I)/NHC complexes with KPO.

A protocol for the mechanochemical synthesis of copper(I)/N-heterocyclic carbene complexes using cheap and readily available KPO as base has been developed. This method employing a ball mill is amenable to typical simple copper(I)/NHC complexes but also to a sophisticated copper(I)/N-heterocyclic carbene complex bearing a guanidine moiety. In this way, the present approach circumvents commonly employed silver(I) complexes which are associated with significant and undesired waste formation and the excessive use of solvents.