Sterically Hindered 2,4,6-Tri-tent-butylpyridinium Salts as Single Hydrogen Bond Donors for Highly Stereoselective Glycosylation Reactions of Glycals

We demonstrate here that the strained and bulky protonated 2,4,6-tri-tert-butylpyridine salts serve as efficient catalysts for highly stereoselective glycosylations of various glycals. Moreover, the mechanism of action involves an interesting single hydrogen bond mediated protonation of glycals and not via the generally conceived Bronsted acid pathway. The counteranions also play a role in the outcome of the reaction.