Iron‐Catalyzed Magnesium‐Mediated Formal Hydroformylation of Alkynes and Alkenes

Abstract Alkynes and alkenes are routinely converted to corresponding synthetically versatile aldehydes using rhodium‐catalyzed hydroformylation. However, rhodium is rare, precious, costly, and depleting at a considerably high rate. Reported here is iron‐catalyzed, magnesium‐mediated, formal hydroformylation of alkynes and alkenes in the absence of syngas. Readily available FeCl 2 in the presence of alkyl magnesium halide, and dimethyl formamide, catalyzes hydroformylation of various alkynes and selectively produces α,β‐unsaturated aldehydes in good to excellent conversion. Mechanistic investigations revealed the presence of vinyl magnesium intermediate, the kinetic study disclosed the first‐order dependence of the reaction on iron loading, and the control experiment authenticated the iron catalyst‘s homogeneous nature. The scope of this methodology was amplified, and 20 alkenes were examined. [Fe(acac) 3 ] in the presence of ligand, alkyl magnesium halide, and dimethyl formamide catalyzed the hydroformylation of alkenes and displayed good to excellent conversion. An earth‐abundant iron catalyst offering a syngas cylinder‐free safe alternative to high‐pressure hydroformylation has been reported.