Deoxygenative\nReduction of 1°, 2° and 3°\nAmides via <i>In Situ</i> Generated Tungsten Cluster Acting\nas H‑Bonding Donor

A protocol of amide-to-amine transformation that is convenient,\nmild, and easy to perform is a long-sought goal from the viewpoint\nof catalysis. Herein, we have utilized easily accessible W(CO)<sub>4</sub>(NCMe)<sub>2</sub> as a precatalyst for the deoxygenative\nreduction of 1°, 2° and 3° amides under mild conditions.\nMechanism studies unraveled that the <i>in situ</i> generated <b>W</b><sub><b>4</b></sub><b>-cluster</b> is potentially\na vital species in activating CO of amides by providing the\nH-bonding network during the catalytic cycle. Significantly, this\ntactic offers a complementary pattern to conventional metal-catalyzed\namide deoxygenative reactions with activation of the CO bond\nvia direct coordination with amide.