Abstract In this article we report that a cationic version of Akiba's BiIII complex catalyzes the reduction of amides to amines using silane as hydride donor. The catalytic system features low catalyst loadings and mild conditions, en route to secondary and tertiary aryl‐ and alkylamines. The system tolerates functional groups such as alkene, ester, nitrile, furan and thiophene. Kinetic studies on the reaction mechanism result in the identification of a reaction network with an important product inhibition that is in agreement with the experimental reaction profiles.
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