The combination of transition-metal catalysis and organocatalysis increasingly offers chemists opportunities to realize diverse unprecedented chemical transformations. By combining iridium with chiral thiourea catalysis, direct enantioselective reductive cyanation and phosphonylation of secondary amides have been accomplished for the first time for the synthesis of enantioenriched chiral a-aminonitriles and aaminophosphonates. The protocol is highly efficient and enantioselective, providing a novel route to the synthesis of optically active a-functionalized amines from the simple, readily available feedstocks. In addition, the reactions are scalable and the thiourea catalyst can be recycled and reused.

Based on the Tf2O‐mediated intermolecular reaction of secondary amides with enamines derived from ketones, a novel approach to β‐enaminones has been developed. The reaction is widely functional group tolerant and highly chemoselective. In the presence of 4 Å molecular sieves, the method can be extended to the one‐pot condensation of secondary amides with ketones for NH β‐enaminones synthesis.

The combination of transition-metal catalysis and organocatalysis increasingly offers chemists opportunities to realize diverse unprecedented chemical transformations. By combining iridium with chiral thiourea catalysis, direct enantioselective reductive cyanation and phosphonylation of secondary amides have been accomplished for the first time for the synthesis of enantioenriched chiral a-aminonitriles and aaminophosphonates. The protocol is highly efficient and enantioselective, providing a novel route to the synthesis of optically active a-functionalized amines from the simple, readily available feedstocks. In addition, the reactions are scalable and the thiourea catalyst can be recycled and reused.