Azasugars| Multicomponent reactions | Nitrilium ion | Isocyanide | Reductive cyclizationA catalytic two-component three-centered (2C3C) Ugi-type reaction was developed for the synthesis of L-1-deoxynojirimycin (DNJ) isomers using a chiron approach. This new and quite mild catalytic system, comprised of phenylphosphinic acid/NaI, was used to synthesize both the L-allo-DNJ and L-altro-DNJ in high yield.