双(二氟甲基)三甲基硅酸盐阴离子：烯醇化酮的亲核二氟甲基化反应中 Me3 SiCF2 H 的关键中间体。
Bis(difluoromethyl)trimethylsilicate Anion: A Key Intermediate in Nucleophilic Difluoromethylation of Enolizable Ketones with Me3 SiCF2 H.
机构信息
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai, 200032, China.
College of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou, Zhejiang, 318000, China.
出版信息
Angew Chem Int Ed Engl. 2016 Oct 4;55(41):12632-6. doi: 10.1002/anie.201605280. Epub 2016 Aug 24.
A pentacoordinate bis(difluoromethyl)silicate anion, Me3 Si(CF2 H)2 , is observed for the first time by the activation of Me3 SiCF2 H with a nucleophilic alkali-metal salt and 18-crown-6. Further study on its reactivity by tuning the countercation effect led to the discovery and development of an efficient, catalytic nucleophilic difluoromethylation of enolizable ketones with Me3 SiCF2 H by using a combination of CsF and 18-crown-6 as the initiation system. Mechanistic investigations demonstrate that (18-crown-6)Cs Me3 Si(CF2 H)2 is a key intermediate in this catalytic reaction.
首次通过亲核碱金属盐和 18-冠-6 对 Me3 SiCF2 H 的活化，观察到五配位双（二氟甲基）硅酸盐阴离子 Me3 Si(CF2 H)2 。通过调节抗衡阳离子效应进一步研究其反应性，发现并开发了一种有效的、催化的烯醇化酮的亲核二氟甲基化方法，使用 CsF 和 18-冠-6 的组合作为引发体系，用 Me3 SiCF2 H 作为试剂。机理研究表明，(18-冠-6)Cs Me3 Si(CF2 H)2 是该催化反应中的关键中间体。
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