title: Direct Transformation of HMF into 2,5-Diformylfuran and 2,5-Dihydroxymethylfuran without an External Oxidant or Reductant.
abstract: The selective transformation of 5-hydroxymethylfurfural (HMF) to valuable 2,5-diformylfuran (DFF) and 2,5-dihydroxymethylfuran (DHMF) is highly desirable but remains a great challenge owing to its tendency to over-oxidation and over-reduction. In this work, HMF is directly converted into DFF and DHMF without external oxidant or reductant through a Meerwein-Ponndorf-Verley-Oppenauer (MPVO) reaction. In such a MPVO process, HMF is used as both oxidant and reductant and DFF and DHMF are simultaneously produced with a 1:1 molar ratio in the presence of a Lewis acid catalyst. Under high initial HMF concentration, a HMF conversion of up to 44.7 % can be reached within 1 h. Moreover, this atom-efficient transformation route for HMF also provides a promising protocol for the crude separation of DHMF products from DFF products, owing to the lower solubility of DHMF compared to DFF in acetonitrile.
authors.affiliation: Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, Collaborative Innovation Centre of Chemistry for Energy Materials, Fudan University, Shanghai, 200433, P.R. China.
authors.forename: Gang
authors.initials: G
authors.lastname: Li
authors.affiliation: Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, Collaborative Innovation Centre of Chemistry for Energy Materials, Fudan University, Shanghai, 200433, P.R. China.
authors.forename: Zhen
authors.initials: Z
authors.lastname: Sun
authors.affiliation: Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, Collaborative Innovation Centre of Chemistry for Energy Materials, Fudan University, Shanghai, 200433, P.R. China.
authors.forename: Yueer
authors.initials: Y
authors.lastname: Yan
authors.affiliation: Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, Collaborative Innovation Centre of Chemistry for Energy Materials, Fudan University, Shanghai, 200433, P.R. China.
authors.forename: Yahong
authors.identifier: 0000-0003-1148-949X
authors.initials: Y
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, Collaborative Innovation Centre of Chemistry for Energy Materials, Fudan University, Shanghai, 200433, P.R. China.
authors.forename: Yi
authors.initials: Y
authors.lastname: Tang
mesh_terms: D002384:Catalysis; D005662:Furaldehyde / Q000031:analogs & derivatives* / Q000737:chemistry; D005663:Furans / Q000138:chemical synthesis / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry*; D010084:Oxidation-Reduction; D019163:Reducing Agents / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry
chemical_list: C000620551:2,5-dihydroxymethylfuran; D005663:Furans; D016877:Oxidants; D019163:Reducing Agents; D012997:Solvents; C008046:5-hydroxymethylfurfural; D005662:Furaldehyde; C476922:2,5-diformylfuran
keywords: 5-hydroxymethylfurfural; biomass conversion; lewis acid; oxidation; reduction