Selective Activation of Fluoroalkenes with N‐Heterocyclic Carbenes: Synthesis of N‐Heterocyclic Fluoroalkenes and Polyfluoroalkenyl Imidazolium Salts,Chemistry - A European Journal

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Selective Activation of Fluoroalkenes with N‐Heterocyclic Carbenes: Synthesis of N‐Heterocyclic Fluoroalkenes and Polyfluoroalkenyl Imidazolium Salts
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2016-05-03 , DOI: 10.1002/chem.201601029
Matthew C. Leclerc ₁ , Serge I. Gorelsky ₁ , Bulat M. Gabidullin ₁ , Ilia Korobkov ₁ , R. Tom Baker ₁

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Selective reactions between nucleophilic N,N′‐diaryl‐heterocyclic carbenes (NHCs) and electrophilic fluorinated alkenes afford NHC fluoroalkenes in high yields. These stable compounds undergo efficient and selective fluoride abstraction with Lewis acids to give polyfluoroalkenyl imidazolium salts. These salts react at Cβ with pyrrolidine to give ammonium fluoride‐substituted salts, which give rise to conjugated imidazolium‐enamine salts through loss of HF. Alternatively, reaction with 4‐(dimethylamino)‐pyridine provides a Cα‐pyridinium‐substituted NHC fluoroalkene. These compounds were studied using multinuclear NMR spectroscopy, mass spectrometry, and X‐ray crystallography. Insight into their electronic structure and reactivity was gained through the use of DFT calculations.

中文翻译：

N-杂环碳烯对氟代烯烃的选择性活化：N-杂环氟代烯烃和多氟烯基咪唑鎓盐的合成

亲核的N，N'-二芳基-杂环卡宾（NHC）与亲电的氟化烯烃之间的选择性反应可提供高收率的NHC氟烯烃。这些稳定的化合物与路易斯酸经过有效的，选择性的氟化物提取，得到多氟烯基咪唑鎓盐。这些盐在Cβ与吡咯烷反应生成氟化铵取代的盐，该盐通过失去HF生成共轭的咪唑鎓-烯胺盐。另外，与4-（二甲基氨基）吡啶反应可得到Cα-吡啶取代的NHC氟代烯烃。使用多核NMR光谱，质谱和X射线晶体学研究了这些化合物。通过使用DFT计算，可以深入了解其电子结构和反应性。

更新日期：2016-05-03

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