Bauer Adriano, Di Mauro Giovanni, Li Jing, Maulide Nuno
Institute of Organic Chemistry, University of Vienna, Währinger Strasse 38, 1090, Vienna, Austria.
Department of Chemistry, Tohoku University, Aoba-ku, 980-8578, Sendai, Japan.
Angew Chem Int Ed Engl. 2020 Oct 5;59(41):18208-18212. doi: 10.1002/anie.202007439. Epub 2020 Aug 17.
The reactivity of iodine(III) reagents towards nucleophiles is often associated with umpolung and cationic mechanisms. Herein, we report a general process converting a range of ketone derivatives into α-cyclopropanated ketones by oxidative umpolung. Mechanistic investigation and careful characterization of side products revealed that the reaction follows an unexpected pathway and suggests the intermediacy of non-classical carbocations.
碘（III）试剂对亲核试剂的反应活性通常与极性翻转和阳离子机制相关。在此，我们报道了一种通过氧化极性翻转将一系列酮衍生物转化为α-环丙烷化酮的通用方法。对副产物的机理研究和详细表征表明，该反应遵循意想不到的途径，并表明存在非经典碳正离子中间体。
