Palladium-catalyzed direct arylation of (hetero)arenes with aryl boronic acids
Palladium-catalyzed direct arylation of (hetero)arenes with aryl boronic acids
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DOI：
10.1002/anie.200704619
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发表时间：
2008-01-01
影响因子：
16.6
通讯作者：
Shi, Zhang-Jie
中科院分区：
文献类型：
--
作者：
Yang, Shang-Dong;Sun, Chang-Liang;Shi, Zhang-Jie
随着化学科学的发展，发现绿色和可持续的转化已被确定为有机化学家面临的主要挑战。仅仅生产有机化合物已不再合适，以最有效和最环保的方式生产产品也很重要。将CÀH债券直接转换为CÀC债券是实现这一目标的一种相对清洁和有效的方法在过去的几十年里，芳香CÀH键转化为CÀC键和CÀX键的方法已经得到了很好的报道，包括利用Ru、Rh和Pd等金属配合物的催化过程在这里，我们描述了一个最近的观察，涉及通过pdii催化富电子（杂）芳烃与芳基硼酸的交叉偶联直接构建联芳基CÀC键。Suzuki-Miyaura偶联是一种强大的方法，在天然产物、合成药物和材料的合成中被广泛应用于构建双芳基通常，反应发生在sp2 CÀX （X= I, Br， OTf等）键与有机硼酸或有机硼酸酯之间最近的发展使偶联更实用，包括使用芳基CÀCl， CÀOTs和烷基CÀX （X=卤化物）键传统的Suzuki-Miyaura偶联需要芳基卤化物，与之相比，芳烃与硼酸的直接芳基化提供了一种形成CÀC键的有效方法。直接芳基化不需要芳基卤化物作为偶联伙伴（尽管大多数芳基硼酸是由卤化物制成的）毫无疑问，直接芳基化不能取代强大的Suzuki-Miyaura偶联，但在某些情况下，这种改进确实解决了三个问题，使其对可持续化学具有吸引力：1)有机卤化物比相应的芳烃昂贵得多；2)卤化物则不然
With the development of chemical sciences, the discovery of green and sustainable transformations has been identified as a major challenge for organic chemists. It is no longer appropriate just to produce the organic compounds, but it is important also to generate the products in the most efficient and environmentally friendly way. Direct transformation of a CÀH bond into a CÀC bond is a relatively clean and efficient method for meeting such goals.[1] In the past few decades, well developed processes have been reported for the transformation of aromatic CÀH bonds to CÀC bonds and CÀX bonds, including catalytic processes utilizing metal complexes such as Ru, Rh, and Pd.[2] Herein we describe a recent observation involving direct construction of biaryl CÀC bonds by a PdII-catalyzed cross coupling of electron-rich (hetero) arenes with aryl boronic acids.Suzuki–Miyaura coupling is a powerful method that has been widely used to construct biaryls in the syntheses of natural products, synthetic drugs, and materials.[3] Generally, reaction occurs between sp2 CÀX (X= I, Br, OTf, etc) bonds and organoboronic acids or organoboronic esters.[4] Recent developments to make the coupling more practical include using aryl CÀCl, CÀOTs, and alkyl CÀX (X= halide) bonds.[5] Compared to the traditional Suzuki–Miyaura coupling, which requires aryl halides, direct arylation of arenes with boronic acids offers an efficient way to form CÀC bonds. Direct arylation does not require aryl halides as the coupling partner (although most of aryl boronic acids are made from halides).[6] Undoubtedly, direct arylation cannot replace the powerful Suzuki–Miyaura coupling, but in some cases this improvement does address three issues that make it attractive for sustainable chemistry: 1) organic halides are much more expensive than the corresponding arenes; 2) halides are not