Dehydration of Amides by Redox‐Active Phenalenyl Based Mn‐Catalyst

A redox‐active phenalenyl ligand coordinated Mn(III)‐complex can be reduced chemically to generate an active catalyst containing a ligand‐centered radical. This chemically reduced Mn‐catalyst shows excellent catalytic reactivity for silylative dehydration of a wide range of primary amides (including late‐stage diversification of various bio‐active molecules) to synthesize nitriles using an inert and inexpensive silane, polymethylhydrosiloxane (PMHS), under mild conditions. Control experiments suggest a radical pathway for the present catalytic reaction, initiated by the ligand‐centered radical.