Blue‐Light‐Driven Iron‐Catalyzed Desulfurization of Thioamides under Hydrosilylation Conditions

Abstract Up to now, there were only few reports on Earth‐abundant transition metal catalyzed reductions of thioamides, one of the explanation of this scarcity being the possible metallic catalyst poisoning due to the adsorption of species containing sulfur. In this contribution, we report the first general iron‐catalyzed hydrogenative desulfurization of tertiary thioamides under hydrosilylation conditions at ambient temperature, the reaction being driven by blue light irradiation. To perform selectively the reduction of thioamides leading to amines (30 examples, 29–97 % yields), highlighting the sole cleavage of the C=S bond, Fe(IMes)(CO) 4 catalyst was used in the presence of phenylsilane under ambient conditions.