Going Beyond the Limits of the Biorenewable Platform: Sodium Dithionite‐Promoted Stabilization of 5‐Hydroxymethylfurfural

: The lack of thermal and storage stability and occurrence of side reactions during the processing of 5-hydroxymethylfurfural (5-HMF) limits its potential as biorenewable platform molecule. The addition of small amounts of the readily available sodium dithionite has a remarkable effect on promoting the stability of 5-HMF and inhibiting side reactions, thus helping to circumvent such limitations. The addition of sodium dithionite led to improvements in thermal stability (120 °C, 4 h, neat; 100 % vs. 37 %), under distillation (yield: 85 % vs. 52 %), and in a wide range of reactions, including 5-HMF synthesis under biphasic conditions (yield: 98 % vs. 67 %; purity: 92 % vs. 83 %) and 5-HMF transformations, such as Knoevenagel condensation with Meldrum's acid (yield: 96 % vs. 74 %), Cannizaro reaction (yield: quantitative vs. 83 %), and condensation with primary diamines to give pyridinium salts (yield: 88 % vs. 60 %).