Trifluoromethylselenylative Difunctionalization of Arynes with [Me₄N][SeCF₃]

Abstract

A general protocol for the trifluoromethylselenylative difunctionalization of aryne with the nucleophilic [Me₄N][SeCF₃] reagent is described. The NiCp₂-catalyzed cross-couplings of o-silylaryl triflates, [Me₄N][SeCF₃], and CsF with H₂O/CH₃CN, D₂O/CD₃CN, and n-C₄F₉I or C₆F₁₃Br or CCl₄ afforded the hydrotrifluoromethylselenylated products, deuterotrifluoromethylselenylated products, and halotrifluoromethylselenylated products, respectively, while the metal-free reaction of o-silylaryl triflates and [Me₄N][SeCF₃] with NFSI provided the bis(trifluoromethylselenylated) products. These reactions allowed for the facile synthesis of diverse difunctionalized SeCF₃ products in good yields, which are unprecedented and difficult to synthesize by other methods. In the Ni-catalyzed reactions, the key aryne intermediate is generated from o-silylaryl triflate in the presence of fluoride ion, coordinates with the nickel catalyst, undergoes ligand exchange with the ^–SeCF₃ anion, and is inserted into the carbon-carbon triple bond to form an o-trifluoromethylselenylaryl-nickel complex, which is then protonated with H₂O/CH₃CN to yield the hydrotrifluoromethylselenylated product, deuterated with D₂O/CD₃CN to produce the deuterotrifluoromethylselenylated product, or halogenated with n-C₄F₉I, C₆F₁₃Br or CCl₄ to afford the halotrifluoromethylselenylated product. In the metal-free reaction, the ^–SeCF₃ anion is first oxidized with NFSI to yield •SeCF₃ radical and fluoride ion, which activates o-silylaryl triflate in situ to form the aryne species, followed by radical addition with •SeCF₃ and subsequent trapping by another •SeCF₃ radical to produce the bis(trifluoromethylselenylated) product. The moisture-sensitive [Me₄N][SeCF₃] salt was successfully tolerated in the reactions with H₂O or D₂O. This work further demonstrated the rich chemistry of [Me₄N][SeCF₃] and the power of aryne-based functionalization as a linchpin step in the production of multi-substituted SeCF₃-arenes.

Keywords

Arynes / Deuterium / Halogen / Trifluoromethylselenylation / Difunctionalization / Nickel / Radical / Cross-Coupling

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2026 SIOC, CAS, Shanghai, & WILEY-VCH GmbH