Fluorination, Trifluoromethylation, and Trifluoromethylthiolation of Alkenes, Cyclopropanes, and Diazo Compounds

This chapter is mainly focused on the application of hypervalent iodine-based reagents used in fluorination and trifluoromethylation reactions, as well as the development of similar type of trifluoromethylthiolation reactions based on dibenzenesulfonimide reagents. The reagents are usually alkenes, cyclopropanes, and diazocarbonyl compounds in which the F/CF3/SCF3 groups are introduced in a bifunctionalization, and in some cases in a trifunctionalization process. The mechanistic similarities and differences for fluoro and trifluoromethyl benziodoxole(on) reagents are studied in detail. Several DFT modeling studies are performed for deeper understanding of the mechanistic features of the reactions. Radiosynthesis of a new hypervalent iodine-based fluorine-18-labeled electrophilic reagent has been developed. This reagent proved to be useful for rapid synthesis of fluorine-18-labeled small molecules, which can be used in positron emission tomography (PET).