Fluoro-Pummerer rearrangement and analogous reactions

Fluorine containing compounds hold huge promise for pharmaceuticals and agrochemicals due to their specific therapeutic potency or pesticide properties. Therefore, the development of selective and efficient methods for the introduction of fluorine or fluorinated groups into organic molecules is one of the most important tasks in organofluorine chemistry today.Oxidative fluorinations of sulfur compounds like the fluoro-Pummerer rearrangement and analogous transformations such as oxidative desulfurization–fluorination reactions reveal mild, selective and efficient pathways toward mono-, di- or trifluorinated organic compounds. This article summarizes the synthetic approaches as well as the scope and limitations of fluoro-Pummerer rearrangements, oxidative desulfurization–fluorination, as well as the oxidative desulfurization–di- and trifluorination reactions. Application of these oxidative fluorination methods gives rise to various α-fluorinated sulfides, gem-difluorides and trifluoromethylated compounds.

Graphical abstractMethods for the preparation of fluorine compounds by fluoro-Pummerer rearrangement of thioethers and related transformations such as various desulfurization–fluorination reactions are reviewed.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Fluoro-Pummerer rearrangement and related reactions are reviewed. ► α-Fluorothioethers are available from sulfoxides by reaction with an electrophile in the presence of a fluoride donor. ► Desulfurization–difluorination is highlighted as a method for the preparation of gem-difluorides. ► Synthesis of gem-difluorides and trifluoromethyl derivatives by oxidative desulfurization–fluorination.