Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University , 29 Wangjiang Road, Chengdu 610064, China.
Chem Rev. 2017 Jul 12;117(13):8787-8863. doi: 10.1021/acs.chemrev.6b00567. Epub 2017 Jan 13.
Transition metal-mediated C-H bond activation and functionalization represent one of the most straightforward and powerful tools in modern organic synthetic chemistry. Bi(hetero)aryls are privileged π-conjugated structural cores in biologically active molecules, organic functional materials, ligands, and organic synthetic intermediates. The oxidative C-H/C-H coupling reactions between two (hetero)arenes through 2-fold C-H activation offer a valuable opportunity for rapid assembly of diverse bi(hetero)aryls and further exploitation of their applications in pharmaceutical and material sciences. This review provides a comprehensive overview of the fundamentals and applications of transition metal-mediated/catalyzed oxidative C-H/C-H coupling reactions between two (hetero)arenes. The substrate scope, limitation, reaction mechanism, regioselectivity, and chemoselectivity, as well as related control strategies of these reactions are discussed. Additionally, the applications of these established methods in the synthesis of natural products and exploitation of new organic functional materials are exemplified. In the last section, a short introduction on oxidant- or Lewis acid-mediated oxidative Ar-H/Ar-H coupling reactions is presented, considering that it is a very powerful method for the construction of biaryl units and polycylic arenes.
过渡金属介导的 C-H 键活化和功能化是现代有机合成化学中最直接、最强大的工具之一。双（杂）芳基是生物活性分子、有机功能材料、配体和有机合成中间体中具有特权的π共轭结构核心。通过 2 倍 C-H 活化，两个（杂）芳基之间的氧化 C-H/C-H 偶联反应为快速组装各种双（杂）芳基提供了宝贵的机会，并进一步探索了它们在药物和材料科学中的应用。本文综述了过渡金属介导/催化的两个（杂）芳基之间氧化 C-H/C-H 偶联反应的基本原理和应用。讨论了这些反应的底物范围、限制、反应机理、区域选择性和化学选择性以及相关的控制策略。此外，还举例说明了这些成熟方法在天然产物合成和新型有机功能材料开发中的应用。在最后一节中，介绍了氧化剂或路易斯酸介导的氧化 Ar-H/Ar-H 偶联反应，考虑到这是构建联芳基单元和多环芳烃的非常强大的方法。
