Access to Fluorine-Containing Asparagine and Glutamine Analogues via Palladium-Catalyzed Formate Reduction

A synthesis of fluorine‐containing asparagine and glutamine analogues via palladium‐catalyzed formate reduction of fluorinated carbonate esters is described. Primary amide moieties at the side‐chain of asparagine and glutamine were successfully replaced with fluoroolefins, which are proposed to be aprotic mimics for amides due to their electronic properties. Fluoro can you go: Fluorine imparts unique properties to organic molecules. Fluoroolefins are proposed to be aprotic mimic for amides due to their electronic properties. Replacement of side‐chain amide moieties of asparagine and glutamine, which play important roles in structure and chemical modification of proteins, with Fluoroolefins has been successfully achieved via Pd‐catalyzed formate reduction of fluoroallyl carbonates.