Visible Light‐Induced Metal‐Free Fluoroalkylations

Abstract Fluoroalkylation is a crucial synthetic process that enables the modification of molecules with fluoroalkyl groups, which can enhance the properties of compounds and have potential applications in medicine and materials science. The utilization of visible light‐induced, metal‐free methods is of particular importance as it provides an environmentally friendly alternative to traditional methods and eliminates the potential risks associated with metal‐catalyst toxicity. This Account describes our studies on visible light‐induced, metal‐free fluoroalkylation processes, which include the use of organic photocatalysts or EDA complexes. We have utilized organophotocatalysts such as Nile red, tri(9‐anthryl)borane, and an indole‐based tetracyclic complex, as well as catalyst‐free EDA chemistry through photoactive halogen bond formation or an unconventional transient ternary complex formation with nucleophilic fluoroalkyl source. A variety of π‐systems including arenes/heteroarenes, alkenes, and alkynes have been successfully fluoroalkylated under the developed reaction conditions.