Rhodium-catalysed C(sp(2))-C(sp(2)) bond formation via C-H/C-F activation.
Rhodium-catalysed C(sp(2))-C(sp(2)) bond formation via C-H/C-F activation.
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铑催化通过 C–H/C–F 活化形成 C(sp2)–C(sp2) 键
DOI：
10.1038/ncomms8472
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发表时间：
2015-06-17
影响因子：
16.6
通讯作者：
Loh TP
中科院分区：
文献类型：
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作者：
Tian P;Feng C;Loh TP
氟烯代表了一类特殊的结构基元，在药物化学中得到了广泛的应用。然而，与以往报道的方法相比，合成氟烯的途径还很不发达，这些方法要么步骤经济，要么反应条件苛刻。在这里，我们提出了一种RhIII催化的C-H/C-F串联活化反应，用于合成(杂化)芳基单氟烯。使用容易获得的二氟烯烃作为亲电剂，提供了一种在无氧化剂条件下将α-氟烯基模体引入(杂环)芳烃的高效且操作简单的方法。此外，乙醇溶剂的使用和原位生成的氟化氢对这种转化是有利的，这表明氢键激活模式参与了C-F键的断裂步骤。
Fluoroalkenes represent a class of privileged structural motifs, which found widespread use in medicinal chemistry. However, the synthetic access to fluoroalkenes was much underdeveloped with previous reported methods suffering from either low step economy or harsh reaction conditions. Here we present a RhIII-catalysed tandem C–H/C–F activation for the synthesis of (hetero)arylated monofluoroalkenes. The use of readily availablegem-difluoroalkenes as electrophiles provides a highly efficient and operationally simple method for the introduction of α-fluoroalkenyl motifs onto (hetero)arenes under oxidant-free conditions. Furthermore, the employment of alcoholic solvent and thein-situgenerated hydrogen fluoride are found to be beneficial in this transformation, indicating the possibility of the involvement of hydrogen bond activation mode with regards to the C–F bond cleavage step.