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Copper-Mediated Trifluoromethylation of Benzylic Csp3 -H Bonds.
Chemistry - A European Journal ( IF 4.3 ) Pub Date : 2018-07-18 , DOI: 10.1002/chem.201802766
Matthew Paeth,William Carson,Jheng-Hua Luo,David Tierney,Zhi Cao,Mu-Jeng Cheng,Wei Liu

Trifluoromethyl‐containing compounds play a significant role in medicinal chemistry, materials and fine chemistry. Although direct C−H trifluoromethylation has been achieved on Csp2−H bonds, direct conversion of Csp3−H bonds to Csp3−CF3 remains challenging. We report herein an efficient protocol for the selective trifluoromethylation of benzylic C−H bonds. This process is mediated by a combination CuIII−CF3 species and persulfate salts. A wide range of methylarenes can be selectively trifluoromethylated at the benzylic positions. A combination of experimental and theoretical mechanistic studies suggests that the reaction involves a radical intermediate and a CuIII−CF3 species as the CF3 transfer reagent.

中文翻译:

铜介导的苄基Csp3-H键的三氟甲基化。

含三氟甲基的化合物在药物化学,材料和精细化学中起着重要作用。尽管已经在Csp 2 -H键上实现了直接的CH三氟甲基化,但是将Csp 3 -H键直接转换为Csp 3 -CF 3仍然具有挑战性。我们在这里报告了苄基CH键的选择性三氟甲基化的有效方案。该过程由Cu III -CF 3物种和过硫酸盐的组合介导。各种各样的甲基​​芳烃可以在苄基位置被选择性地三氟甲基化。实验和理论机理研究的组合表明,该反应涉及自由基中间体和Cu III-CF 3种类作为CF 3转移试剂。
更新日期:2018-07-18
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