A Simple and Versatile Amide Directing Group for C-H Functionalizations.
A Simple and Versatile Amide Directing Group for C-H Functionalizations.
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DOI：
10.1002/anie.201600791
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发表时间：
2016-08-26
期刊：
影响因子：
--
通讯作者：
Yu JQ
中科院分区：
文献类型：
--
作者：
Zhu RY;Farmer ME;Chen YQ;Yu JQ
在存在多个C-H键的情况下，在单个和关键位点实现选择性C-H活化可以提供强大且通常有用的逆合成断开。在这种情况下，导向基团用作指南针，使用距离和几何形状作为强有力的识别参数来将过渡金属引导到C-H键，以区分近端和远端C-H键。然而，定向基团的安装和移除是实际的缺点。为了提高这种方法的效用，可以从三个方向寻求解决办法。第一，简化导向基团;第二，使用常见的官能团或保护基团作为导向基团;第三，通过瞬时共价键将导向基团连接到基底以使导向基团具有催化性。本文综述了一种非常简单而又广泛适用于Pd（II）、Rh（III）和Ru（II）催化剂的导向基团，即N-甲氧基酰胺（CONHOMe）的合理开发。通过社区的集体努力，已经开发了使用这种类型的简单导向基团的广泛的C-H活化转化。本文综述了一种简单而通用的酰胺导向基团的发展和出现，用于使用Pd，Rh和Ru催化的广泛的C-H官能化反应。最初选择N-甲氧基酰胺作为Pd催化的sp2和sp3 C-H活化的导向基团是基于碱金属羧酸盐与Pd催化剂配位的研究。这个简单的导向基团的应用和修饰也导致了一系列新的Rh（III）催化的C-H活化反应的发现。基于芳基C-H活化的烯烃对映选择性氢芳基化反应的成功开发是一个亮点。最后，使用具有这种定向基团的更便宜的钌催化剂显著提高了这些定向C-H活化反应的实用性。
Achieving selective C–H activation at a single and strategic site in the presence of multiple C–H bonds can provide a powerful and generally useful retrosynthetic disconnection. In this context, the directing group serves as a compass to guide the transition metal to C–H bonds using distance and geometry as powerful recognition parameters to distinguish between proximal and distal C–H bonds. However, the installation and removal of directing groups is a practical drawback. To improve the utility of this approach, one can seek solutions in three directions. First, simplifying the directing group; Second, use of common functional groups or protecting groups as directing groups; Third, attaching the directing group to substrates via a transient covalent bond to render directing groups catalytic. This review describes the rational development of an extremely simple and yet broadly applicable directing group for Pd(II), Rh(III) and Ru(II) catalysts, namely, the N-methoxy amide (CONHOMe). Through collective efforts in the community, a wide range of C–H activation transformations using this type of simple directing groups has been developed. This review describes the development of and emergence of a simple and versatile amide directing group for a wide range of C–H functionalization reactions using Pd, Rh and Ru catalysis. The initial choice of the N-methoxy amide as the directing group for Pd-catalyzed sp2 and sp3 C–H activation is based upon the studies on the alkali carboxylate coordination with Pd catalysts. The application and modification of this simple directing group has also led to the discovery of an array of novel Rh(III)-catalyzed C–H activation reactions. The successful development of enantioselective hydroarylation of olefins based aryl C–H activation is a highlight. Finally, the use of cheaper ruthenium catalysts with this directing group significantly improves the practicality of these directed C–H activation reactions.
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