Transition‐Metal‐Free Perfluoroalkylation of N‐Thiophthalimides or N‐Thioimides to Access Perfluoroalkyl Sulfides

A practical and efficient trifluoromethylation of readily available and bench stable N‐Thiophthalimides and N‐Thioimides with Ruppert‐Prakash reagent (TMS‐CF3) is described. The reaction proceeds at room temperature and only requires NaOAc as the mild promoter to prepare a series of trifluoromethyl thioethers in good to excellent yields. Both aryl and alkyl derivates are well trifluoromethylated under transition‐metal‐free reaction conditions. Moreover, the reaction features with scale‐up synthesis and late‐stage modification of bioactive molecule.