2 - Electrophilic reactions in the synthesis of organofluorine compounds

Abstract

The electrophilic fluorination and fluoroalkylation reactions, fluoroalkylthiolation reactions, and fluoroalkoxylation reactions have found applications in the synthesis of pharmaceuticals, agrochemicals, fine chemicals, and fluorinated materials. Selectfluor and N-fluorobenzenesulfonimide are the widely used electrophilic fluorinating agents and are used in the preparation of corticosteroids, α-fluorination of amino acids, and in the enantioselective fluorination of the allylsilanes and enolsilyl ethers. Electrophilic trifluoromethylations of a wide variety of alcohols, amines, thiols, alkynes, and aromatics have found applications in the synthesis of pharmaceuticals and materials. Electrophilic trifluoromethylthiolations of amines, alkynes, and carbonyl compounds are also useful in the late-stage modification of pharmaceuticals. This chapter outlines synthetic methods based on the electrophilic fluorination and fluoroalkylation reactions that have broad scope and applications in the synthesis of pharmaceuticals and materials.