芳基
化学
电泳剂
亲核细胞
卤化物
氧化加成
卤代芳基
杂原子
配体(生物化学)
铜
催化作用
药物化学
光化学
立体化学
有机化学
戒指(化学)
生物化学
烷基
受体
作者
Connor P. Delaney,Eva Lin,Qin-An Huang,Isaac Furay Yu,Guodong Rao,Lizhi Tao,Ana Jed,Serena Fantasia,Kurt Püntener,R. David Britt,John F. Hartwig
出处
期刊:Science
[American Association for the Advancement of Science (AAAS)]
日期:2023-09-07
卷期号:381 (6662): 1079-1085
被引量:21
标识
DOI:10.1126/science.adi9226
摘要
Copper complexes are widely used in the synthesis of fine chemicals and materials to catalyze couplings of heteroatom nucleophiles with aryl halides. We show that cross-couplings catalyzed by some of the most active catalysts occur by a mechanism not previously considered. Copper(II) [Cu(II)] complexes of oxalamide ligands catalyze Ullmann coupling to form the C–O bond in aryl ethers by concerted oxidative addition of an aryl halide to Cu(II) to form a high-valent species that is stabilized by radical character on the oxalamide ligand. This mechanism diverges from those involving Cu(I) and Cu(III) intermediates that have been posited for other Ullmann-type couplings. The stability of the Cu(II) state leads to high turnover numbers, >1000 for the coupling of phenoxide with aryl chloride electrophiles, as well as an ability to run the reactions in air.
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