D-fructose, a biomass-derived carbohydrate has been identified as an environmentally benign C synthon in the preparation of synthetically useful 2-hydroxymethylbenzimidazole derivatives by coupling with 1,2-phenylenediamines. Proof of concept was established by synthesizing 23 examples using BF .OEt (20 mol%), TBHP (5.5 M, decane) (1.0 equiv.) in CH CN at 90 °C for 1 h. The pivotal features of this method include metal-free conditions, short time, good functional group tolerance, gram scale feasibility and the synthesis of benzimidazole fused 1,4-oxazine. Control studies with conventional C synthons did not produce the desired product, thus suggesting a new reaction pathway from D-fructose.