Sustainable Synthesis of Acyl Fluoride via 1,3‐Chelation‐Assisted Transhalogenation and Its Application in the Valorization of Biomass‐Derived Alcohol in Aqueous System

We developed an environmentally friendly method for synthesizing acyl fluorides and achieving the selective mono‐acylation of water‐soluble alcohols using acyl fluorides in green media. Our method offers substantial advantages over the existing technologies for acyl fluoride production, particularly in terms of cost and environmental impact. Notably, our approach is augmented by an unusual 1,3‐chelation via transhalogenation, and the use of an eco‐friendly solvent and a simple base aligns with the principles of sustainable chemistry. We also explored the direct and highly efficient mono‐acylation of biomass‐derived water‐soluble alcohols, such as ethylene glycol and glycerol, in the presence of water. The key arrangements, such as the role of the K₂CO₃ base and unusual 1,3‐chelation between acyl fluoride and potassium ion, were characterized by HRMS and NMR spectroscopic analysis, and controlled experiments. These findings underscore the effectiveness of this method and provide deeper insights into the reaction mechanism.