Sulfur-based organofluorine reagents for selective fluorination, fluoroalkylation, and fluoroolefination reactions

A good partnership between “soft” sulfur and “hard” fluorine creates a rich chemistry for the introduction of structurally diverse fluorine or fluoroalkyl groups into organic molecules. The combination of sulfur and fluorine chemistry enables the synthesis of bench-stable sulfur-based fluorination reagents, fluoroalkyl sulfones, sulfoximine, sulfoxides, sulfinate, and sulfides. Notably, the reactivity of these reagents could be well-tuned by the incorporation of different substituents on sulfur, or changing the number of fluorine atoms (fluoroalkyl groups) in sulfur-based organofluorine reagents under different reaction conditions. Thus, a series of valuable fluorination, fluoroalkylation, fluoroolefination, fluoroalkanesulfonylation, fluoroalkanesufinylation, and fluoroalkanethiolation reactions via nucleophilic, electrophilic, and radical modes have been realized. The present review encompasses and highlights the polarity transduction, different C − S bond cleavages, radical fluoroalkylation reactions, and unique fluorine effects of sulfur-based organofluorine reagents.