Halogen‐Bond‐Promoted Hydroxyperfluoroalkylation of Olefins with Molecular Oxygen under Visible‐Light Irradiation

Abstract Fluorinated organic compounds are indispensable, and the development of perfluoroalkylation reaction is an important topic of concern. In this paper, we present the generation of an amine‐promoted visible‐light‐induced hydroxyperfluoroalkylation reaction of olefines using molecular oxygen as a hydroxy source. This reaction is caused by the formation of perfluoroalkyl radicals due to visible‐light irradiation to halogen‐bonded complex of a tertiary amine and a perfluoroalkyl iodide. This transformation is applicable for various types of electron‐deficient olefins and styrene, and various fluoroalkyl iodides are acceptable as well. This visible‐light induced, metal‐free reaction using inexpensive and readily available reagents is a sustainable method for the synthesis of fluorine‐containing compounds.