Synthesis of 1-deoxy-l-gulonojirimycin (l-guloDNJ) and 1-deoxy-d-talonojirimycin (d-taloDNJ) Original Research Article

Carbohydrate based syntheses of azasugars with unusual configurations viz. 1,5-dideoxy-1,5-imino-l-gulitol (l-guloDNJ) and 1,5-dideoxy-1,5-imino-l-talitol (l-taloDNJ) are reported, from d-mannose and d-fructose, respectively. The key steps in both syntheses involved reductive aminative cyclizations. Thus, l-guloDNJ was obtained by reduction of 2,3;4,6-di-O-isopropylidene-5-O-p-toluenesulfonyl-d-mannononitrile with LiAlH4 in DME to give the protected azasugar which upon hydrolysis with HCl afforded crystalline l-guloDNJ as the HCl salt in 29% overall yield. Reduction of 6-azido-1-O-tert-butyldimethylsilyl-2,3-O-isopropylidene-β-d-ribohexulofuranose obtained from d-fructose in six steps, followed by treatment with HCl, afforded l-taloDNJ as an HCl salt in ∼10% overall yield.