3,4‐Dicyano‐2,5,6‐Trifluorophenyl Glycosides as Electron‐Deficient Fluoroarene Glycosyl Donors for Chemical Glycosylation

Here, we present 3,4‐dicyano‐2,5,6‐trifluorophenyl glycosides as bench‐stable, and reactive electron‐deficient fluoroarene based glycosyl donors that can be prepared in one‐step and be activated with catalytic amounts of TMSOTf. The glycosylation reaction conditions show tolerance towards acid/base sensitive protecting groups and have a different substrate scope with 68‐89% yields. The electron‐deficient fluoroarene‐containing glycosyl donor enables the construction of O‐ and C‐glycosides using both free alcohols and silylated alcohols, as well as C‐ nucleophiles as acceptors.