Exploiting the Strained Ion-Pair Interactions of Sterically Hindered Pyridinium Salts Toward S2 Glycosylation of Glycosyl Trichloroacetimidates.

We demonstrate here that strained and sterically hindered protonated 2,4,6-tri--butylpyridinium (TTBPy) tetrafluoroborate, a crystalline, bench stable salt serves as a mild and efficient organocatalyst for the S2 type displacement of glycosyl trichloroacetimidates toward the stereoselective synthesis of both α- and β-glycosides. The strained ion-pair interactions between the sterically hindered pyridinium cation and the tetrafluoroborate anion infuse unusual reactivity to the ions resulting in the unique anion assisted activation of alcohol. This mild activation of alcohol facilitates the S2 type displacement of glycosyl αtrichloroacetimidates into β-glycosides in a highly diastereoselective manner. These unique interactions were established based on extensive infrared and H, F, B NMR studies and theoretical studies.