Synthesis of Perfluoro Alkyl/Alkenyl Aryl Sulfide: C−S Coupling Reaction Using Hexafluoropropylene Dimer (HFPD) as a Building Block

Efficient approaches to perfluoroalkyl/alkenyl aryl sulfides were accomplished by a C−S coupling reaction under mild conditions. Hexafluoropropylene dimer was employed as a versatile building block for the perfluoroalkylation and perfluoroalkenylation of thiophenol. The application of the synthetic strategy was demonstrated by the high‐yield transformation of a broad range of aryl derivatives. A plausible mechanistic explanation was proposed to elaborate the differences between the two reaction pathways. The methodology provides straightforward and convenient access to aryl sulfides constituting C6 perfluoroalkyl and perfluoroalkenyl substituents. Hexafluoropropylene dimer (HFPD) was directly employed to synthesize perfluoro alkyl/alkenyl aryl sulfides. A variety of thiophenol substrates were conveniently chlorinated by N‐chlorosuccinimide (NCS); afterwards, C6 perfluoroalkyl was introduced in the presence of cesium fluoride (Path A). Moreover, the C6 perfluoroalkenyl was directly constructed by inorganic base‐catalyzed nucleophilic substitution (Path B).