State Key Laboratory of Bioorganic & Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2017 Dec 18;56(51):16136-16179. doi: 10.1002/anie.201701690. Epub 2017 Nov 15.
Metal-catalyzed cross-coupling reactions belong to the most important transformations in organic synthesis. Copper catalysis has received great attention owing to the low toxicity and low cost of copper. However, traditional Ullmann-type couplings suffer from limited substrate scopes and harsh reaction conditions. The introduction of several bidentate ligands, such as amino acids, diamines, 1,3-diketones, and oxalic diamides, over the past two decades has totally changed this situation as these ligands enable the copper-catalyzed coupling of aryl halides and nucleophiles at both low reaction temperatures and catalyst loadings. The reaction scope has also been greatly expanded, rendering this copper-based cross-coupling attractive for both academia and industry. In this Review, we have summarized the latest progress in the development of useful reaction conditions for the coupling of (hetero)aryl halides with different nucleophiles. Additionally, recent advances in copper-catalyzed coupling reactions with aryl boronates and the copper-based trifluoromethylation of aromatic electrophiles will be discussed.
金属催化的交叉偶联反应属于有机合成中最重要的转化之一。由于铜的毒性低、成本低，铜催化受到了极大的关注。然而，传统的乌尔曼型偶联反应由于底物范围有限和反应条件苛刻而受到限制。在过去的二十年中，几种双齿配体的引入，如氨基酸、二胺、1,3-二酮和草酰二酰胺，完全改变了这种情况，因为这些配体使得芳基卤化物和亲核试剂在低反应温度和催化剂负载下的铜催化偶联成为可能。反应范围也大大扩大，使得这种基于铜的交叉偶联反应在学术界和工业界都很有吸引力。在这篇综述中，我们总结了开发用于（杂）芳基卤化物与不同亲核试剂偶联的有用反应条件的最新进展。此外，还将讨论芳基硼酸酯的铜催化偶联反应以及铜催化的芳香族亲电试剂的三氟甲基化反应的最新进展。
