Sustainable Aerobic Transamidation and Esterification of N-Heteroaryl Amides by Heterogeneous Copper Catalyst

• first example of heterogeneous catalyzed transamidation of secondary amides • recyclable/green needle-shape copper nanoparticles catalyst • C-H and C-N bond double activations • high functional group tolerance Transamidation of secondary amides via heterogeneous strategy has remained an unsolved problem. Here we report a novel and efficient approach for transamidation and esterification of ubiquitous N -heteroaryl amides with various amines and alcohols that exploits an engineered heterogeneous supported copper nanoparticles catalyst. This method overcomes the difficulty of heterogeneous catalysts, which can only achieve transamidation of primary amide driven by the emission of ammonia gas. A broad diversity of N -heteroaryl amides containing quinolin-2-yl, isoquinolin-1-yl, pyrazin-2-yl and pyridin-2-yl directing groups convert into corresponding α-ketoamides and α-ketoesters using needle-shape copper nanoparticles supported on γ-Al 2 O 3 as heterogeneous catalyst. This environmentally benign, catalyst recyclable and easy-to-handle catalysis methodology will have great application prospects in the pharmaceutical synthesis and biological or chemical industry.