The impact of oxacarbenium ion conformers on the stereochemical outcome of glycosylations.

The search for stereoselective glycosylation reactions has occupied synthetic carbohydrate chemists for decades. Traditionally, most attention has been focused on controlling the S(N)2-like substitution of anomeric leaving groups as highlighted by Lemieux's in situ anomerization protocol and by the discovery of anomeric triflates as reactive intermediates in the stereoselective formation of beta-mannosides. Recently, it has become clear that also S(N)1-like reaction pathways can lead to highly selective glycosylation reactions. This review describes some recent examples of stereoselective glycosylations in which oxacarbenium ions are believed to be at the basis of the selectivity. Special attention is paid to the stereodirecting effect of substituents on a pyranosyl ring with an emphasis on the role of the C-5 carboxylate ester in the condensations of mannuronate ester donors. Copyright 2010 Elsevier Ltd. All rights reserved.