Palladium‐Catalyzed Synthesis of Carboxylic Acid Anhydrides from Alkenes via in situ Generated Carboxylic Acids

We herein present a carbonylative strategy to synthesize acid anhydrides from alkenes via in situ generated carboxylic acids. Formic acid (FA) reacts with alkene and CO under catalytic conditions to generate carboxylic acids. With our established palladium‐based catalytic reaction conditions and modulating the alkene:formic acid ratio to at least 2:1, symmetric acid anhydrides were effectively generated. The catalytic process was applied to various alkenes, simple as well as with various functional groups, to give moderate to excellent yields as observed with NMR and isolation of the corresponding (linear) amide produced on derivatization. Furthermore, one‐pot derivatization of the reaction mixtures provides direct access to various acyl‐based molecules including phenolic esters, primary amides, thioesters and ketones, which otherwise require special conditions for their synthesis via carbonylation.