A Versatile, Electrophilic Reagent for Monofluoromethylthiolation†

Comprehensive Summary A new electrophilic monofluoromethylthiolating reagent N ‐fluoromethylthiophthalimide PhthSCH 2 F 1 was developed. Reagent 1 could be readily synthesized from easily available starting materials benzyl mercaptan and CH 2 FCl in three steps. N ‐Fluoromethylthiophthalimide 1 is a powerful electrophilic monofluoromethylthiolating reagent that allows the monofluoromethylthiolation of a wide range of nucleophiles including alkynes, aryl/vinyl boronic acids, electron‐rich heteroarenes, β ‐ketoesters and oxindoles, as well as thiols under mild conditions.