Iron‐Catalyzed Alkoxycarbonylation of Alkyl Bromides via a Two‐Electron Transfer Process

Abstract Transition metal‐catalyzed carbonylative cross‐coupling reactions are some of the most widely used methods in organic synthesis. However, despite the obvious advantages of iron as an abundant and low toxicity transition metal catalyst, its practical application in carbonylation reaction remains largely unexplored. Here we report our recent study on Fe‐catalyzed alkoxycarbonylation of alkyl halides. Mechanistic studies indicate that the reaction is catalyzed by an in situ generated Fe 2− complex. This low‐valent iron species activates alkyl bromides via a distinctive two‐electron transfer (TET) process, whereas it proceeds via a single electron transfer (SET) process for alkyl iodides which is consistent with literature.