Silicon-Assisted Ferrier Rearrangement in Preparation of C3-Silyl Glycosides

Herein, we report a Lewis acid catalyzed Ferrier rearrangement glycosylation strategy using the α-effect of C3-silylated glucal donors. The dimethylphenylsilyl group at the C3 position promotes the reaction where the unactivated free hydroxy group at the C3 position acts as a leaving group. An inexpensive 5 mol % loading of AlCl₃ was employed as the catalyst to achieve the desired transformation. This work provides the first efficient access to C3-silyl glycosides. Further, diversification of the obtained products is achieved through modified Fleming-Tamao oxidation and olefin functionalization.