8 - Oxidative Trifluoromethylation and Trifluoromethylthiolation

Abstract

Recently, extensive attention has been devoted toward the development of efficient and versatile methods for introducing the CF3 group into various organic molecules. Direct trifluoromethylation reactions have become one of the most efficient and important approaches for constructing carbon–CF3 bonds. Traditionally, nucleophilic trifluoromethylation reaction involves the electrophile and the CF3 anion, whereas electrophilic trifluoromethylation reaction involves the nucleophile and CF3 cation. In 2010, we proposed the concept of oxidative trifluoromethylation: the reaction of nucleophilic substrates and nucleophilic trifluromethylation reagents in the presence of oxidants. In this chapter, we will describe the recent studies of oxidative trifluoromethylation reactions of various nucleophiles with trifluoromethyl anion precursors in the presence of oxidants. Furthermore, the oxidative trifluoromethylthiolation reactions to construct carbon-SCF3 bonds will be included. Finally, other oxidative fluoroalkylations (such as oxidative difluoromethylation, pentafluoroethylation, and heptafluoroisopropylation) will be introduced.