First Synthesis of DL-2-C-Hydroxymethyl-3-Pentulose in the Formose Reaction

The formose reactions2 in N,N-dimethylformamide (DMF) catalyzed by 2-(dimethylamino)ethanol and thiamine hydrochloride, have been found to give rise to dihydroxyacetone and DL-glycero-tetrulose selectively at 1.1 M and 3.0 M of formaldehyde concentration, respectively. In our consecutive study on the formose reaction in DMF, it has been fortunately found that the distribution of products is able to be controlled by the amount of water added to the reaction mixture. We describe herein the first example of the favored formation of DL-2-C-hydroxymethyl-3-pentu-lose (GP-191) in the formose reaction using DMF-H2O solvent, and it's isolation and structure elucidation.