NAP Ether Mediated Intramolecular Aglycon Delivery: A Unified Strategy for 1,2‐cis‐Glycosylation

Abstract A methodology directed towards the stereoselective construction of 1,2‐ cis ‐glycosides through naphthylmethyl (NAP) ether mediated intramolecular aglycon derivery (IAD) has been developed. Stereospecific constructions of various 1,2‐ cis linkages, as in β‐mannopyrano‐, β‐arabinofurano‐, and α‐glucopyranosides, were achieved through NAP‐IAD. This methodology was successfully applied to the synthesis of Glcα(1→2)‐Glcα(1→3)‐Glcα(1→3)Man (Glc 3 Man 1 ), the nonreducing terminal structure of the tetradecasaccharide Glc 3 Man 9 GlcNAc 2 , a common precursor of all N ‐linked glycans.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)