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

AbstractA 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.Keywords: Sulfurfluorinefluorinationfluoroalkylationfluoroolefination Disclosure statementThe authors have no conflict of interest.Additional informationFundingThis work was supported by the National Key Research and Development Program of China (2021YFF0701700) and the National Natural Science Foundation of China (22271299 and 22261132514).