Zhao Weizhao, Huang Xin, Zhan Yaling, Zhang Qifeng, Li Dongyang, Zhang Yage, Kong Lichun, Peng Bo
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004, China.
Angew Chem Int Ed Engl. 2019 Nov 25;58(48):17210-17214. doi: 10.1002/anie.201909019. Epub 2019 Oct 15.
Herein we describe the dearomatization of aryl iodanes through an unprecedented "rearrangement/addition" sequence. The process consists of two stages. First, a rapid [3,3] sigmatropic rearrangement of the aryl iodane with an α-stannyl nitrile affords a highly electrophilic dearomatized intermediate at -78 °C. A low-temperature rearrangement then enables the unstable dearomatized species to be trapped in situ with various nucleophiles. As a consequence, the reaction not only breaks the aromaticity of the aryl iodane but also sequentially installs two different functional groups, thus resulting in a polysubstituted alicyclic product.
在此，我们描述了通过前所未有的“重排/加成”序列实现芳基碘鎓盐的去芳构化反应。该过程由两个阶段组成。首先，芳基碘鎓盐与α-锡基腈在-78°C下发生快速的[3,3] 迁移重排，生成一种高度亲电的去芳构化中间体。然后，低温重排使得不稳定的去芳构化物种能够与各种亲核试剂原位捕获。因此，该反应不仅打破了芳基碘鎓盐的芳香性，还依次引入了两个不同的官能团，从而得到多取代的脂环族产物。
