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

• Published in: ChemCatChem Vol. 15; no. 3
• Main Authors: Tewari, Tanuja, Kumar, Rohit, Chikkali, Samir H.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 08.02.2023
• Subjects: Aldehydes; Alkenes; Alkynes; Catalysts; Conversion; Dimethylformamide; hydroformylation; iron catalysis; Iron chlorides; Magnesium; Rhodium; Synthesis gas
• ISSN: 1867-3880; 1867-3899
• DOI: 10.1002/cctc.202201394

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 FeCl2 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. Precious and rare rhodium has been the work‐horse metal for traditional hydroformylation. Herein, we report an earth‐abundant iron catalyst for the formal hydroformylation of alkynes and alkenes. The iron catalyst transforms alkynes and alkenes to aldehydes in the presence of magnesium reagent and dimethylformamide, thus offering a syngas cylinder‐free safe alternative to high‐pressure hydroformylation.