Abstract Earth‐abundant transition metal catalysis has emerged as an important alternative to noble transition metal catalysis in hydrogenation reactions. However, there has been no Earth‐abundant transition metal catalyzed hydrogenation of thioamides reported so far, presumably due to the poisoning of catalysts by sulfur‐containing molecules. Herein, we described the first manganese‐catalyzed hydrogenative desulfurization of thioamides to amines or imines. The key to success is the use of MnBr(CO)5 instead of commonly‐employed pincer‐manganese catalysts, together with simple NEt3 and CuBr. This protocol features excellent selectivity on sole cleavage of the C=S bond of thioamides, in contrast to the only known Ru‐catalyzed hydrogenation of thioamides, and unprecedented chemo‐selectivity tolerating vulnerable functional groups such as nitrile, ketone, aldehyde, ester, sulfone, nitro, olefin, alkyne and heterocycle, which are usually susceptible to common hydride‐type reductive protocols.
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