Rhodium catalyzed chelation-assisted C-H bond functionalization reactions.
Rhodium catalyzed chelation-assisted C-H bond functionalization reactions.
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DOI：
10.1021/ar200190g
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发表时间：
2012-06-19
影响因子：
18.3
通讯作者：
Ellman, Jonathan A.
中科院分区：
文献类型：
--
作者：
Colby, Denise A.;Tsai, Andy S.;Bergman, Robert G.;Ellman, Jonathan A.
在过去的几十年里，研究人员在有机金属化学领域取得了显着的进展。金属催化的交叉偶联反应的发展代表了化学合成的范式转变，今天的合成化学家可以很容易地从大量的起始化合物中获得碳-碳和碳-杂原子键。尽管我们不能低估这些方法的重要性，但进行这些反应所需的预官能化增加了成本并降低了起始试剂的可用性。使用C-H键活化代替预官能化已经为经典的交叉偶联反应提供了一种诱人的替代方案。随着底物和催化剂设计的创新性进展，研究人员已经遇到了与C-H键官能化反应的发展相关的选择性和反应性的挑战。关于基于空间效应、酸度、电子和导向基团效应的选择性的文献报道现在很多。我们的小组已经开发了一系列利用螯合导向基团的C-H键官能化反应，本报告综述了我们在这一领域的进展。在C-H键官能化中使用螯合控制提供了关于底物范围和全合成应用的几个优点。可预测性和对底物固有立体电子学的依赖性降低通常导致具有广泛适用性的选择性和高产率转化。可以选择螯合部分的性质以在随后的加工中充当功能性手柄。我们的工作开始于Rh（I）催化剂在分子内芳香族C-H环化，我们进一步发展，包括对映选择性转化。将这种化学方法应用于在α，β-不饱和亚胺中发现的简单烯属C-H键，可以获得高度取代的烯烃、吡啶和哌啶。我们观察到与Rh（III）催化剂的互补反应性，并开发了与未活化烯烃的氧化偶联。对Rh（III）催化剂的进一步研究使我们开发了将C-H键偶联到极化π键（如亚胺和异氰酸酯中的π键）的方法。在几种情况下，我们已经开发的螯合控制的C-H键官能化的方法已被应用到复杂分子，如天然产物的全合成，突出了这些方法在有机合成中的实用性。
Over the last several decades, researchers have achieved remarkable progress in the field of organometallic chemistry. The development of metal-catalyzed cross-coupling reactions represents a paradigm shift in chemical synthesis, and today synthetic chemists can readily access carbon-carbon and carbon-heteroatom bonds from a vast array of starting compounds. Although we cannot understate the importance of these methods, the required pre-functionalization to carry out these reactions adds cost and reduces the availability of the starting reagents. The use of C-H bond activation in lieu of pre-functionalization has presented a tantalizing alternative to classical cross-coupling reactions. Researchers have met the challenges of selectivity and reactivity associated with the development of C-H bond functionalization reactions with an explosion of creative advances in substrate and catalyst design. Literature reports on selectivity based on steric effects, acidity, and electronic and directing group effects are now numerous. Our group has developed an array of C-H bond functionalization reactions that take advantage of a chelating directing group, and this Account surveys our progress in this area. The use of chelation control in C-H bond functionalization offers several advantages with respect to substrate scope and application to total synthesis. The predictability and decreased dependence on the inherent stereoelectronics of the substrate generally result in selective and high yielding transformations with broad applicability. The nature of the chelating moiety can be chosen to serve as a functional handle in subsequent elaborations. Our work began with the use of Rh(I) catalysts in intramolecular aromatic C-H annulations, which we further developed to include enantioselective transformations. The application of this chemistry to the simple olefinic C-H bonds found in α,β-unsaturated imines allowed access to highly substituted olefins, pyridines, and piperidines. We observed complementary reactivity with Rh(III) catalysts and developed an oxidative coupling with unactivated alkenes. Further studies on the Rh(III) catalysts led us to develop methods for the coupling of C-H bonds to polarized π bonds such as those in imines and isocyanates. In several cases the methods that we have developed for chelation-controlled C-H bond functionalization have been applied to the total synthesis of complex molecules such as natural products, highlighting the utility of these methods in organic synthesis.
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影响因子：
16.6
作者：
Chen, Xiao;Engle, Keary M.;Wang, Dong-Hui;Yu, Jin-Quan
通讯作者：
Yu, Jin-Quan
影响因子：
1.6
作者：
Kakiuchi, F;Sato, T;Murai, S
通讯作者：
Murai, S
影响因子：
1.6
作者：
Fujii, N;Kakiuchi, F;Murai, S
通讯作者：
Murai, S
影响因子：
--
作者：
Kakiuchi, F;Le Gendre, P;Murai, S
通讯作者：
Murai, S
影响因子：
5.2
作者：
Fischer, Joshua;Savage, G. Paul;Coster, Mark J.
通讯作者：
Coster, Mark J.