Institute of Advanced Synthesis (IAS), School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University, 30 South Puzhu Road, Nanjing, 211816, P. R. China.
Angew Chem Int Ed Engl. 2017 Nov 20;56(47):14918-14922. doi: 10.1002/anie.201708505. Epub 2017 Oct 9.
An unprecedented rhodium(III)-catalyzed hydroarylation of α,α-difluoromethylene alkynes with N-pivaloxyl aroylamides through sequential C-H activation and aryl migration is detailed herein. A large array of α,α-difluoromethylene alkynes and N-pivaloxyl aryl amides were amenable to this transformation, thus providing a novel synthetic protocol for the construction of difluorinated 2-alkenyl aniline derivatives in high yields and with excellent regioselectivity. Notably, unique fluorine effects were found to underlie the thus unconventional reaction manifold.
本文详细介绍了铑(III)催化的α,α-二氟亚甲基炔烃与 N-特戊酰基芳酰胺通过顺序 C-H 活化和芳基迁移的空前氢芳化反应。大量的α,α-二氟亚甲基炔烃和 N-特戊酰基芳酰胺都适用于这种转化，因此为构建高收率和优异区域选择性的二氟代 2-烯基苯胺衍生物提供了一种新的合成方法。值得注意的是，发现独特的氟效应是这种非常规反应机理的基础。
