Conformationally restricted donors for stereoselective glycosylation.

In nucleophilic reactions using sugars as electrophiles, i.e., glycosyl donors, their conformation affects the generation rate or stability of the glycosyl cation intermediates and determines at which side of the S_N2-S_N1 borderline and at what rate the reaction occurs. In addition, changes in the conformation create the steric or stereoelectronic effects of the substituents, which also change the reaction rate and stereoselectivity. Bulky silyl protecting groups, uronic acid esters, and transannular structures have been utilized to change the conformation. Consequently, reactions with unique reactivities and stereoselectivities have been developed. In this chapter, a discussion of the reaction mechanisms relating stereoselectivity to conformation is provided.