Photocatalytic fluoroalkyl radical-initiated construction of fluorinated heterocycles: mechanisms and applications

Abstract

Fluorine-containing heterocycles hold exceptional value across pharmaceuticals, agrochemicals, and materials science owing to fluorine's distinctive electronic effects, lipophilicity, and capacity to modulate bioactivity. Their streamlined synthesis has therefore become a central pursuit in contemporary organic chemistry. Photocatalysis, characterized by mild, sustainable conditions and finely tunable redox properties, provides innovative strategies for constructing fluorinated heterocycles via fluoroalkyl radical pathways. Notably, recent advances in photochemically induced fluoroalkyl radical strategies have enabled modular heterocycle synthesis through single-electron transfer, electron donor-acceptor complex activation, or energy-transfer mechanisms. This review consolidates progress since 2018, systematically dissecting the mechanisms of photocatalytic fluoroalkyl radical-driven formation of five-, six-, and seven-membered fluorinated heterocycles. It further provides an in-depth analysis of emerging trends and application prospects, aiming to establish a theoretical foundation for heterocyclic synthesis and fluorine chemistry, while guiding the rational design of novel, functional fluorinated heterocyclic molecules.