Development of Electrophilic Radical Perfluoroalkylation of Electron‐Deficient Olefins

Abstract

Fluorinated organic compounds have attracted significant attention over the past few decades owing to their unique properties and versatility. An established method for the synthesis of fluorinated organic compounds involves radical perfluoroalkylation reactions towards double bonds. In this radical pathway, electrophilic perfluoroalkyl radicals exhibit excellent reactivity towards electron‐rich olefins. Therefore, several splendid perfluoroalkylation reactions of electron‐rich olefins have been reported. However, there are only a few examples of reaction involving electron‐deficient olefins because of their poor electronic compatibility with perfluoroalkyl radicals. This review focuses on the reports that challenge this long‐standing issue. Radical perfluoroalkylation/bifunctionalization reactions of electron‐deficient olefins are described according to the radical generation methods.

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

“…of substrates 1 h – 1 p , respectively. Reactions with low yields ( 1 h – 1 p ) demonstrated the existence of a residual substrate [10] …”

“…Reactions with low yields (1 h-1 p) demonstrated the existence of a residual substrate. [10] Subsequently, the investigation on the reaction of styrenes [8] favorably showed its applicability to unsubstituted styrenes Scheme 2. Scope of conjugated olefins.…”

“…It has hardly been applied to electron‐deficient olefins [8q,r] such as methacrylates and acrylates. This may be because such electron‐deficient olefins are incompatible with electron‐deficient perfluoroalkyl radicals [10] and are highly polymerizable.…”

Hydroxy- and Hydro-Perfluoroalkylation of Styrenes by Controlling the Quenching Cycle of Eosin Y

“…All reactions were performed under the argon atmosphere. 1 H, 13 C, and 19 F NMR spectra were recorded on a JEOL GSX-400 spectrometer (Jeol, Akishima, Tokyo, Japan) Scheme 4. Proposed mechanism for hydroxy-and hydro-perfluoroalkylation.…”

“…Indeed, many examples of perfluoroalkylation to electron-rich olefins have been reported. However, few studies have reported on perfluoroalkylation with conjugated olefins [13], particularly styrene, due to the likelihood of side reactions such as oligomerization, polymerization, and nucleophilic trapping.…”