Conversion of Glucose in CPL‐LiCl to 5‐Hydroxymethylfurfural

5‐Hydroxymethylfurfural (HMF), an important versatile sugar derivative, is also considered a key intermediate between petroleum‐based industrial organic chemistry and bio‐based carbohydrate chemistry. Here, we report that caprolactam (CPL) containing lithium chloride (LiCl) is a privileged solvent that enables the synthesis of the renewable platform chemical 5‐hydroxymethylfurfural (HMF) from purified glucose. Metal halides in CPL‐LiCl are catalysts, among which CrCl 3 , CrCl 2 , SnCl 4 and SnCl 2 are found to be uniquely effective, leading to the conversion of glucose to HMF with yields of 55% –67%. The simplicity of this chemical transformation of glucose contrasts markedly with the complexity of extant processes and provides a new paradigm for the use of biomass as a raw material for a renewable energy and chemical industries.