Modular Synthesis of Fluoro-Substituted Furan Compounds via Controllable Fluorination of Biomass-Based 5-HMF and Its Derivatives.

Abstract

5-Hydroxymethylfurfural (5-HMF) is regarded as one of the most promising platform feedstocks for producing valuable chemicals, fuels, and materials. In this study, we present a controllable fluorination technique for biomass-based 5-HMF and its oxygenated derivatives. This technique allows us to synthesize mono-fluoromethyl, difluoromethyl, and acylfluoro-substituted furan compounds by adjusting experimental conditions such as different fluorine sources and mole ratio. To gain a deeper understanding the reactivity order, we conducted intermolecular and intramolecular competition experiments. The results revealed that the hydroxyl group exhibited the highest reactivity, followed by the aldehyde group. This finding provides important theoretical support and opens up the possibility of selective fluorination. The reaction offers several advantages, including mild conditions, no need for inert gas protection, and easy operation. Furthermore, the fluoro-substituted furan compounds can be further transformed for the preparation of drug analogs, offering a new route for the high-value utilization of biomass molecules.