Deoxygenative Reduction of 1°, 2° and 3° Amides via In Situ Generated Tungsten Cluster Acting as H‑Bonding Donor

A protocol of amide-to-amine transformation that is convenient, mild, and easy to perform is a long-sought goal from the viewpoint of catalysis. Herein, we have utilized easily accessible W(CO)₄(NCMe)₂ as a precatalyst for the deoxygenative reduction of 1°, 2° and 3° amides under mild conditions. Mechanism studies unraveled that the in situ generated W₄-cluster is potentially a vital species in activating CO of amides by providing the H-bonding network during the catalytic cycle. Significantly, this tactic offers a complementary pattern to conventional metal-catalyzed amide deoxygenative reactions with activation of the CO bond via direct coordination with amide.