Tandem Fe/Zn or Fe/In Catalysis for the Selective Synthesis of Primary and Secondary Amines via Selective Reduction of Primary Amides

Abstract Tandem iron/zinc or iron/indium‐catalysed reductions of various primary amides to amines under hydrosilylation conditions are reported under visible light activation. By a simple modification of the nature of the co‐catalyst (Zn(OTf) 2 vs In(OTf) 3 ), Fe(CO) 4 (IMes) can promote the highly chemoselective reduction of primary amides into primary amines (21 examples, up to 93 % isolated yields) and secondary amines (8 examples, up to 51 % isolated yields), respectively. Notably, both benzamide and alkanamide derivatives can be reduced.