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Halogen and Chalcogen Cation Pools Stabilized by DMSO. Versatile Reagents for Alkene Difunctionalization

Ashikari, Yosuke, Shimizu, Akihiro, Nokami, Toshiki, Yoshida, Jun-ichi
Journal of the American Chemical Society 2013 v.135 no.43 pp. 16070-16073
alkenes, carbonyl compounds, cations, dimethyl sulfoxide, electrochemistry, methanol, oxidation, triethylamine
Halogen and chalcogen cations (X⁺ = Br⁺, I⁺, ArS⁺, and ArSe⁺) were generated by low-temperature electrochemical oxidation in the presence of dimethyl sulfoxide (DMSO) and were accumulated in the solution. DFT calculations indicated that DMSO stabilizes these cations by coordination. The complexes of I⁺ with one and two DMSO molecules were observed by cold-spray-ionization MS analyses. The stability of the resulting cation pools of X⁺ increased in the order of Br⁺ < I⁺ < ArS⁺ < ArSe⁺, which could be explained in terms of the electronegativity of X. The cation pools served as versatile reagents for organic synthesis; the reactions with alkenes gave β-X-substituted alkoxysulfonium ions, which were converted to the corresponding carbonyl compounds by the treatment with triethylamine, whereas the treatment with methanol gave the corresponding alcohols. The reactions with aminoalkenes and 1,6-dienes gave the cyclized products.