Industrial Routes from Sugars and Biomass to CMF and Other 5‐(Halomethyl)furfurals

Abstract

The synthesis of 5‐(halomethyl)furfurals (XMFs, X = F, Cl, Br, I), including 5‐(chloromethyl)furfural (CMF), 5‐(bromomethyl)furfural (BMF), 5‐(iodomethyl)furfural (IMF), and 5‐(fluoromethyl)furfural (FMF), from biomass represents a pivotal advancement in renewable chemistry and engineering. Harnessing waste biomass as a raw material offers a sustainable alternative to fossil‐based resources, mitigating environmental degradation and addressing pressing energy needs. CMF and BMF, characterized by their enhanced stability over the hydroxyl analog, 5‐(hydroxymethyl)furfural (HMF), exhibit promise as renewable building blocks for scale‐up and commercialization. The surge in research interest, particularly from 2010 to 2024, reflects a growing recognition of XMFs' potential as novel platform chemicals. This review highlights the evolution of XMF synthesis methods, focusing on their transformation from saccharides and lignocellulosic biomass. Mechanistic insights and experimental setups are scrutinized for industrial feasibility and scalability, shedding light on technical challenges and avenues for further research. The analysis underscores the burgeoning significance of XMFs in the transition towards sustainable chemical production, emphasizing the importance of process optimization and mechanistic understanding for commercial deployment.