Enabling Nucleophilic Substitution Reactions of Activated Alkyl Fluorides through Hydrogen Bonding
Enabling Nucleophilic Substitution Reactions of Activated Alkyl Fluorides through Hydrogen Bonding
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DOI：
10.1021/ol400765a
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发表时间：
2013-05-03
期刊：
影响因子：
5.2
通讯作者：
Paquin, Jean-Francois
中科院分区：
文献类型：
--
作者：
Champagne, Pier Alexandre;Pomarole, Julien;Paquin, Jean-Francois
研究发现，水作为助溶剂的存在使活化的烷基氟化物反应成为双分子亲核取代反应。DFT计算表明，激活是通过更强的F中心点中心点中心点H2O相互作用和减小的C-F键延伸率来稳定过渡结构的，而不是简单的过渡态静电稳定。总的来说，研究结果提出了一种通过h键激活C-F键的独特策略。
It was discovered that the presence of water as a cosolvent enables the reaction of activated alkyl fluorides for bimolecular nucleophilic substitution reactions. DFT calculations show that activation proceeds through stabilization of the transition structure by a stronger F center dot center dot center dot H2O interaction and diminishing C-F bond elongation, and not simple transition state electrostatic stabilization. Overall, the findings put forward a distinct strategy for C-F bond activation through H-bonding.