Recent Advances in Photochemical and Photoelectrochemical Fluoroalkylation: Direct Use of Fluoroalkyl Carboxylic Acids

Abstract

Extensive research has been dedicated to developing sustainable and practical methodologies for installing fluoroalkyl groups into organic molecules, as such structural modifications can effectively tune the physicochemical and pharmacological properties of drug candidates. Despite significant advances, most established fluoroalkylation protocols still suffer from inherent drawbacks: conventional fluoroalkylating reagents are often expensive, thermally or chemically labile, and difficult to handle. Furthermore, their practical implementation usually requires stoichiometric redox chemicals to facilitate the generation of operative fluoroalkylating intermediates, compromising functional group tolerance and atom economy and ultimately restricting applicability in large‐scale synthesis. This review summarizes recent advances in fluoroalkylations using widely available fluoroalkyl carboxylic acids as direct fluoroalkyl radical precursors, highlighting the unique merits, synthetic scope, and future potential of this emerging strategy.