Department of Chemistry, University of California, Berkeley, CA, 94720, USA.
Angew Chem Int Ed Engl. 2021 Apr 6;60(15):8203-8211. doi: 10.1002/anie.202015654. Epub 2021 Mar 3.
Here, we report a class of ligands based on oxalohydrazide cores and N-amino pyrrole and N-amino indole units that generates long-lived copper catalysts for couplings that form the C-O bonds in biaryl ethers. These Cu-catalyzed coupling of phenols with aryl bromides occurred with turnovers up to 8000, a value which is nearly two orders of magnitude higher than those of prior couplings to form biaryl ethers and nearly an order of magnitude higher than those of any prior copper-catalyzed coupling of aryl bromides and chlorides. This ligand also led to copper systems that catalyze the coupling of aryl chlorides with phenols and the coupling of aryl bromides and iodides with primary benzylic and aliphatic alcohols. A wide variety of functional groups including nitriles, halides, ethers, ketones, amines, esters, amides, vinylarenes, alcohols and boronic acid esters were tolerated, and reactions occurred with aryl bromides in pharmaceutically related structures.
在这里，我们报告了一类基于乙二醛腙核心和 N-氨代吡咯和 N-氨代吲哚单元的配体，它们生成了用于形成联苯醚中 C-O 键的长寿命铜催化剂。这些 Cu 催化的酚与芳基溴化物的偶联反应的转化率高达 8000，这一数值比以前形成联苯醚的偶联反应高近两个数量级，比以前任何 Cu 催化的芳基溴化物和氯化物的偶联反应高近一个数量级。这种配体还导致了铜体系能够催化芳基氯化物与酚的偶联以及芳基溴化物和碘化物与一级苄基和脂肪醇的偶联。包括腈、卤代物、醚、酮、胺、酯、酰胺、乙烯基芳烃、醇和硼酸酯在内的各种官能团都能被容忍，并且反应能够在具有药物相关结构的芳基溴化物上进行。
