Transition-Metal-Free Dehalogenative 1,2-Dichalcogenation of Internal Fluoroalkyl Alkenes
Chi Zhang , Wei Han , Li-Dan Zhang , Zhi-Liang Shen , Mengtao Ma , Xue-Qiang Chu
Chinese Journal of Chemistry ›› 2025, Vol. 43 ›› Issue (23) : 3266 -3272.
Fluoroalkene and 1,2-enedichalcogenide represent two classes of valuable structures with wide applications, yet methods for their direct integration remain unknown. Herein, we report a dehalogenative 1,2-dichalcogenation reaction of internal fluoroalkyl alkenes and readily available disulfides, thiols, or diselenides for the synthesis of diverse fluoroalkenyl 1,2-enedichalcogenides. Multiple carbon-halogen bonds in perfluoroalkyl-containing alkenyl iodides can be selectively cleaved under mild and transition-metal-free conditions. This protocol features a broad substrate scope, good scalability, and the ability to modify complex molecules. Mechanistic studies revealed that the key step in the reaction is the formation of a reactive fluoroallene, which is readily attacked by nucleophilic thiolate anions to achieve an unconventional defluorinative chalcogenation.
Alkene / Disulfide / Thiol / Dehalogenation / Sulfenylation / Defluoroalkenylation / Chalcogenation / Defluorination
2025 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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