Radical Perfluoroalkylation of Aliphatic Substrates

Abstract

A selection of perfluoroalkylation reactions of aliphatic substrates that display methodological and synthetic amplitude will be studied, giving examples of their applications and mechanistic details. An array of synthetic approaches for fluoroalkylation reactions are documented; in particular, radical protocols are prominent among perfluoroalkylation methods. To that effect, addition reactions of perfluoroalkyl radicals RF (RF=CnF2n+1, n > 1) to unsaturated organic substrates serve as one of the most direct and efficacious ways to access fluoroalkylated scaffolds. The syntheses of perfluoroalkyl-substituted vinyl, alkynyl, and allylic compounds; the syntheses of perfluoroalkyl-substituted hydro-, iodo-, and oxy-perfluoroalkylated alkanes and olefins; the syntheses of perfluoroalkyl-substituted carbonyl compounds; the syntheses of perfluoroalkyl-substituted enamides, amides, thioamides, and hydrazones; and multicomponent perfluoroalkylation reactions will be studied. While there are a number of accomplished reports on organofluorination, we aim to provide an overview of radical-involved perfluoroalkylation reactions of aliphatic substrates, covering examples from 2018 to early 2023, as summarized in Tables 1-4.