Cross-Coupling and Related Reactions: Connecting Past Success to the Development of New Reactions for the Future
Cross-Coupling and Related Reactions: Connecting Past Success to the Development of New Reactions for the Future
复制标题
DOI：
10.1021/acs.organomet.8b00720
复制
发表时间：
2019-01-14
期刊：
影响因子：
2.8
通讯作者：
Hazari, Nilay
中科院分区：
文献类型：
--
作者：
Campeau, Louis-Charles;Hazari, Nilay
交叉偶联反应是近50年前发现的，广泛应用于工业和学术界。尽管交叉偶联反应现在代表了成熟的技术，但在这一领域仍有大量的研究旨在改善这些反应的范围，开发更有效的催化剂，并使反应更实用。在本教程中，提供了一个简短的背景交叉耦合反应，然后在交叉耦合研究在过去20年的主要进展进行了描述。这些包括开发用于交叉偶联的改进配体和预催化剂，以及将交叉偶联反应扩展到更广泛的亲电试剂。例如，交叉偶联反应现在常见于spa杂化的亲电试剂以及酯、酰胺、醚和氮丙啶底物。对于许多这些更现代的基底，传统的钯基催化剂的效率低于基于第一行过渡金属如镍的系统。传统的交叉偶联反应也激发了一系列相关反应的发展，例如交叉亲电偶联和脱羧偶联以及基于金属光氧化还原化学的偶联。这些新反应的发展可能与30年前的传统交叉偶联反应处于同一阶段，本教程强调了用于改进交叉偶联反应的许多相同策略也可能适用于使新反应更加实用。
Cross-coupling reactions, which were discovered almost 50 years ago, are widely used in both industry and academia. Even though cross-coupling reactions now represent mature technology, there is still a significant amount of research in this area that aims to improve the scope of these reactions, develop more efficient catalysts, and make reactions more practical. In this tutorial, a brief background to cross-coupling reactions is provided, and then the major advances in cross coupling research over the last 20 years are described. These include the development of improved ligands and precatalysts for cross-coupling and the extension of cross-coupling reactions to a much wider range of electrophiles. For example, cross-coupling reactions are now common with spa-hybridized electrophiles as well as ester, amide, ether, and aziridine substrates. For many of these more modern substrates, traditional palladium-based catalysts are less efficient than systems based on first-row transition metals such as nickel. Conventional cross-coupling reactions have also inspired the development of a range of related reactions, such as cross-electrophile and decarboxylative couplings as well as couplings based on metallaphotoredox chemistry. The development of these new reactions is probably at the same stage as traditional cross-coupling reactions 30 years ago, and this tutorial highlights how many of the same strategies used to improve cross-coupling reactions may also be applicable to making the new reactions more practical.