Versatile Palladium-Catalyzed Approach to Acyl Fluorides and Carbonylations by Combining Visible Light- and Ligand-Driven Operations

We describe the development of a general palladium-catalyzed carbonylative method to synthesize acyl fluorides from aryl, heteroaryl, alkyl, and functionalized organic halides. Mechanistic analysis suggests that the reaction proceeds via the synergistic combination of visible light photoexcitation of Pd(0) to induce oxidative addition with a ligand-favored reductive elimination. These together create a unidirectional catalytic cycle that is uninhibited by the classical effect of carbon monoxide coordination. Coupling the catalytic formation of acyl fluorides with their subsequent nucleophilic reactions has opened a method to perform carbonylation reactions with unprecedented breadth, including the assembly of highly functionalized carbonyl-containing products.

Automated summary

We have developed a general palladium-catalyzed method to synthesize acyl fluorides from different types of compounds. Mechanistic analysis suggests that the reaction proceeds through the combination of visible light photoexcitation of Pd(0) with a ligand-favored reductive elimination, resulting in a unidirectional catalytic cycle. Coupling this catalytic method with nucleophilic reactions allows for a broad range of carbonylation reactions, including the synthesis of highly functionalized products.