Telluronium-Catalyzed Halogenation Reactions: Chalcogen-Bond Activation of N-Halosuccinimides and Catalysis

The ability of triaryltelluronium salts to interact with N-halosuccinimides (NXS) through chalcogen bonding (ChB) in the solid state and in solution is demonstrated herein. Cocrystals of the triaryltelluronium bearing two CF₃ electron-withdrawing groups per aryl ring with N-chloro-, N-bromo- and N-iodosuccinimide (respectively NCS, NBS and NIS) were analyzed by X-ray diffraction, evidencing a ChB between tellurium and the carbonyl group of NXS. This ChB was confirmed in solution by NMR spectroscopy, especially by ¹²⁵Te NMR titration experiment, which allowed the determination of the association constant (K_a) between the telluronium and NBS. The so-obtained K_a value of 17.3±0.6 M^-1 indicated a moderate interaction in solution because of the competitive role of the solvent. The strength of the Te⋅⋅⋅O ChB was however sufficient enough to promote the catalytic halofunctionalization of aromatics and of alkenes such as the intra- and intermolecular haloalkoxylation and haloesterification of alkenes.