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 W 4 -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.