HFC - 125对羰基化合物的五氟乙基化反应：钾阳离子与甘醇二甲醚的包封作用
Pentafluoroethylation of Carbonyl Compounds by HFC-125 the Encapsulation of the K Cation with Glymes.
作者信息
Fujihira Yamato, Hirano Kazuki, Ono Makoto, Mimura Hideyuki, Kagawa Takumi, Sedgwick Daniel M, Fustero Santos, Shibata Norio
机构信息
Department of Life Science and Applied Chemistry, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan.
Department of Nanopharmaceutical Sciences, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan.
出版信息
J Org Chem. 2021 Apr 16;86(8):5883-5893. doi: 10.1021/acs.joc.1c00298. Epub 2021 Mar 29.
A simple protocol to overcome the explosive pentafluoroethylation of carbonyl compounds by HFC-125 is described. The use of potassium (K) bases with triglyme or tetraglyme as a solvent safely yields the pentafluoroethylation products in good to high yields. The experimental results suggest that an encapsulation of the K cation by glymes as K(glyme) inhibits the contact between the K cation and the reactive anionic pentafluoroethyl counterion, preventing their transformation into KF and explosive tetrafluoroethylene (TFE). The generation of sterically demanding [K(G3)] and [K(G4)] is an effective way as an unstable pentafluoroethyl anion reservoir.
描述了一种克服HFC-125使羰基化合物发生爆炸性五氟乙基化反应的简单方法。使用钾（K）碱并以三甘醇二甲醚或四甘醇二甲醚作为溶剂，能够安全地以良好至高收率得到五氟乙基化产物。实验结果表明，以K(甘醇二甲醚)形式存在的甘醇二甲醚对K阳离子的包裹作用抑制了K阳离子与反应性五氟乙基阴离子抗衡离子之间的接触，从而防止它们转化为KF和爆炸性的四氟乙烯（TFE）。生成空间位阻较大的[K(G3)]和[K(G4)]是作为不稳定五氟乙基阴离子储存库的有效方法。
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