Nitrogen ligands in copper-catalyzed arylation of phenols : Structure/activity relationships and applications
Nitrogen ligands in copper-catalyzed arylation of phenols : Structure/activity relationships and applications
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DOI：
10.1002/adsc.200600628
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发表时间：
2007-08
影响因子：
5.4
通讯作者：
Armelle Ouali;J. Spindler;A. Jutand*;M. Taillefer
中科院分区：
文献类型：
--
作者：
Armelle Ouali;J. Spindler;A. Jutand*;M. Taillefer
尽管配体/铜催化的亲核试剂芳基化反应在有机化学中具有重要意义，但使配体在这些反应中有效的结构和电子特征至今尚未确定。在这项工作中，几个双齿配体涉及吡啶和/或亚胺氮结合位点，如我们的铅配体1已被合成，并在苯酚芳基化测试，以期突出螯合物的结构和它们的功效之间的关系。这项研究使我们能够更精确地确定每种类型的N-结合位点在催化过程中的作用，并发现新的有效配体。其中，亚氨基吡啶6a具有价格便宜、易于制备、产率高的优点，具有很大的工业应用前景。这里介绍了其应用领域的一些例子。在未来，这项工作的发展可以允许更合理的设计有效的配体在芳基化反应，而不诉诸经典的配体筛选。
In spite of the importance of ligand/ copper-catalyzed arylations of nucleophiles in organic chemistry, the structural and electronic features that make a ligand efficient in these reactions have not been determined until now. In this work, several bidentate ligands involving pyridine and/or imine nitrogen binding sites such as our lead ligand 1 have been synthesized, and tested in phenol arylations with a view to highlight relationships between the structure of the chelates and their efficacy. This study allowed us to more precisely define the role of each type of N-binding site during the catalytic process, and to discover new efficient ligands. Among them, the iminopyridine 6a, which is cheap and easy-to-prepare in high yield, is very attractive for industrial applications. Some examples of its field of application are presented here. In the future, the development of this work could allow a more rational design of efficient ligands in arylation reactions, without resorting to classical ligand screening.