Controlling the Reaction Networks for Efficient Conversion of Glucose into 5‐Hydroxymethylfurfural

Biomass-derived hexose constitutes the main component of lignocellulosic biomass for producing value-added chemicals and biofuels. However, the reaction network of hexose is complicated, which makes the highly selective synthesis of one particular product challenging in biorefinery. This Review focuses on the selective production of 5-hydroxymethylfurfural (HMF) from glucose on account of its potential significance as an important platform molecule. The complex reaction network involved in glucose-to-HMF transformations is briefly summarized. Special emphasis is placed on analyzing the complexities of feedstocks, intermediates, (side-) products, catalysts, solvents, and their impacts on the reaction network. The strategies and representative examples for adjusting the reaction pathway toward HMF by developing multifunctional catalysts and promoters, taking advantage of solvent effects and process intensification, and synergizing all measures are comprehensively discussed. An outlook is provided to highlight the challenges and opportunities faced in this promising field. It is expected to provide guidance to design practical catalytic processes for advancing HMF biorefinery.