AbstractHighly diastereoselective nucleophilic additions to cyclic nitrones derived from L‐malic acid and D‐arabinose have been used for the construction of enantiomerically pure polyhydroxylated pyrrolidines. The synthetic strategy adopted was based on an oxidation/reduction protocol involving hydroxylamine/nitrone pairs and demonstrates the use of reagent‐ and substrate‐derived stereocontrol. In most cases reactions took place with total diastereoselectivity and in quantitative yield, with no purification being necessary. By this strategy, 2‐(hydroxymethyl)‐, 2‐(aminomethyl)‐, and 2‐aryl‐substituted polyhydroxylated pyrrolidines have been prepared with abundant configurational diversity. The use of appropriate substrates and reagents allowed for approaches to DMDP, 6‐deoxy‐DMDP, DAB‐1, CYB‐3, nectrisine and radicamine B. Several analogues of these compounds with inverted configuration at one or more stereocenters were also prepared.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)