Transition-Metal-Free Catalytic Hydrodefluorination of Polyfluoroarenes by Concerted Nucleophilic Aromatic Substitution with a Hydrosilicate
Transition-Metal-Free Catalytic Hydrodefluorination of Polyfluoroarenes by Concerted Nucleophilic Aromatic Substitution with a Hydrosilicate
复制标题
DOI：
10.1002/anie.201708003
复制
发表时间：
2017-12-18
影响因子：
16.6
通讯作者：
Ogoshi, Sensuke
中科院分区：
文献类型：
--
作者：
Kikushima, Kotaro;Grellier, Mary;Ogoshi, Sensuke
描述了多氟芳烃的无过渡金属催化加氢脱氟 (HDF) 反应。该反应涉及作为关键中间体的氢硅酸盐的直接氢化物转移，该中间体是由氢硅烷和氟化物盐生成的。消除的氟化物使氢硅酸盐再生以完成催化循环。色散校正 DFT 计算表明 HDF 反应通过协同亲核芳香取代 (CSNAr) 过程进行。
A transition-metal-free catalytic hydrodefluorination (HDF) reaction of polyfluoroarenes is described. The reaction involves direct hydride transfer from a hydrosilicate as the key intermediate, which is generated from a hydrosilane and a fluoride salt. The eliminated fluoride regenerates the hydrosilicate to complete the catalytic cycle. Dispersion-corrected DFT calculations indicated that the HDF reaction proceeds through a concerted nucleophilic aromatic substitution (CSNAr) process.