Catalytic, Enantioselective Fluorination Reactions

Toste, F. D.; Thornbury, R.


The unique properties conferred by the incorporation of fluorine into organic molecules has resulted in the widespread use of organofluorine compounds in the pharmaceutical and agrochemical industries. In contrast, organofluorine compounds are exceedingly rare in nature. The dearth of chiral pool organofluorine compounds necessitates the development of stereoselective methods for the incorporation of carbon–fluorine bonds into organic molecules. A wide variety of catalytic, enantioselective fluorination methods have been developed to address this challenge, including Lewis acid catalysis, organocatalysis, transition metal catalysis, and phase transfer catalysis. Using these methods, carbonyl compounds, alkenes, allylic electrophiles, aziridines, and epoxides have been engaged in catalytic, enantioselective fluorination reactions. This chapter provides a comprehensive review of the methods available for the catalytic, enantioselective construction of carbon–fluorine bonds and is subdivided into electrophilic and nucleophilic fluorination reactions. The chapter also provides a comparison with diastereoselective transformations and enantioselective functionalization reactions of fluorinated substrates.