Huang Xin, Zhang Yage, Zhang Chaoshen, Zhang Lei, Xu Ying, Kong Lichun, Wang Zhi-Xiang, Peng Bo
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004, China.
School of Chemical Sciences, University of the Chinese Academy of Sciences, Beijing, 100049, China.
Angew Chem Int Ed Engl. 2019 Apr 23;58(18):5956-5961. doi: 10.1002/anie.201900745. Epub 2019 Mar 27.
Presented herein is an intriguing effect of fluorine, and it allows difluoroenol silyl ethers to couple with aryliodanes in a redox-neutral manner to afford ortho-iodo difluoroalkylated arenes. The remaining iodide group provides a versatile platform for converting the products into various valuable difluoroalkylated arenes. The reaction shows excellent functional-group compatibility and broad substrate scope. A DFT mechanistic study suggests that the fluorine effect facilitates a subtle nucleophilic attack of the oxygen atom of enol silyl ethers onto aryliodanes, therefore leading to a rearrangement.
本文展示了氟的一种有趣效应，它能使二氟烯醇硅醚与芳基碘烷以氧化还原中性的方式偶联，生成邻碘二氟烷基化芳烃。剩余的碘基团为将产物转化为各种有价值的二氟烷基化芳烃提供了一个通用平台。该反应显示出优异的官能团兼容性和广泛的底物范围。一项密度泛函理论（DFT）机理研究表明，氟效应促进了烯醇硅醚的氧原子对芳基碘烷的微妙亲核进攻，从而导致重排。
