Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, School of Pharmaceutical Sciences, Chongqing University, Chongqing, 401331, P.R. China.
State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, China.
Angew Chem Int Ed Engl. 2021 Apr 26;60(18):10211-10218. doi: 10.1002/anie.202100049. Epub 2021 Mar 24.
The first iron-catalyzed defluorosilylation of unactivated gem-difluoroalkenes was developed, delivering gem-disilylated alkenes and (E)-silylated alkenes with excellent efficiency. This protocol features good functional group compatibility and excellent regio- and stereoselectivity, enabling the late-stage silylation of biologically relevant compounds, thus providing good opportunities for applications in medicinal chemistry. Preliminary mechanistic studies and DFT calculations reveal that a nucleophilic addition and elimination of the second C-F bond might be involved in the disilylation catalytic system, demonstrating unusual reactivity characteristics of iron catalysis.
首次发展了铁催化的未活化偕二氟烯烃的脱氟硅基化反应，以高收率得到了偕二硅基化烯烃和（E）-硅基化烯烃。该反应具有良好的官能团兼容性和优异的区域及立体选择性，能够实现生物相关化合物的后期硅基化，从而为在药物化学中的应用提供了良好的机会。初步的机理研究和 DFT 计算表明，在双硅化催化体系中可能涉及到第二个 C-F 键的亲核加成和消除，这展示了铁催化的不寻常反应活性特征。
