Water‐Assisted Fe(CO) ₅ Catalyzed Transfer Hydrodesulfurization of Thioamides

Herein, an efficient method for a chemo‐selective hydrodesulfurization of thioamides to secondary and tertiary amines was achieved via a selective Fe(CO) 5 ‐catalyzed cleavage of CS bond in water. This work presents a unique and rare methodology, as it utilizes water as a surrogate of hydrogen to functionalize various thioamide derivatives. Moreover, α , α ‐dideuterated amine was also prepared using inexpensive deuterium oxide (D 2 O). DFT calculations were performed to verify the mechanistic insights of the reaction.