Transition‐Metal‐Free Dehalogenative 1,2‐Dichalcogenation of Internal Fluoroalkyl Alkenes

Comprehensive Summary 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.