Stereocontrolled Synthesis of 2‐Fluorinated C‐Glycosides

A systematic study of the addition of C‐based nucleophiles to fluorinated lactones based on 2‐deoxy‐2‐fluoro‐d‐pyranoses is disclosed. This high yielding, α‐selective process was found to be independent on the nature or configuration [(R)‐C(sp(3))–F, (S)‐C(sp(3))–F] of the substituent at C2. Representative, fluorinated analogues of Trehalose, Carminic acid, and the spirocyclic cores of Tofogliflozin and Papulacandin D are also reported. These glycomimics constitute a valuable series of (19)F NMR active probes for application in structural biology.