Effect of electron-withdrawing protecting groups at remote positions of donors on glycosylation stereochemistry

Abstract

Here we review the equatorial β-directing effects of electron-withdrawing protecting groups at remote positions of mannopyranosyl donors, mannuronate donors, rhamnopyranosyl donors, and 2,6- dideoxyglucopyranosyl donors. We discuss the equatorial α-directing effect of an electron-withdrawing group at the N-5 position of sialyl donors. The proposed mechanism and origin of some of the equatorial β-directing effects are described. We also review the effects of potentially participating, electron-withdrawing protecting groups at remote positions of glycopyranosyl and glycofuranosyl donors on the glycosylation stereochemistries. Further, we present substantial evidence in favor of the remote participation by the electron-withdrawing protecting groups and also include reports that are opposed to remote participation. © 2011 Springer-Verlag Berlin Heidelberg.