Xie Yuanhao, Zhang Li, Ritter Tobias
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany.
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
Angew Chem Int Ed Engl. 2025 Jun 10;64(24):e202502441. doi: 10.1002/anie.202502441. Epub 2025 Apr 14.
Herein, we present a cross-coupling reaction of arylthianthrenium salts at a late stage with diverse (hetero)aryl (pseudo)halides under reductive conditions, in which a palladium(0) catalyst differentiates between two aryl electrophiles based on the different rates of oxidative addition of arylthianthrenium salts and aryl halides for selective umpolung. A measured near-zero Hammett rho value is consistent with oxidative addition of the arylthianthrenium salts to palladium(0) being insensitive to substituent effects, which enables reaction with structurally and electronically diverse arylthianthrenium salts. In addition, we show the robustness of this method by coupling of two complex fragments that would otherwise be difficult to access in a single step.
在此，我们展示了芳基噻蒽鎓盐在还原条件下与多种（杂）芳基（拟）卤化物在后期进行的交叉偶联反应，其中钯（0）催化剂基于芳基噻蒽鎓盐和芳基卤化物氧化加成速率的不同，区分两种芳基亲电试剂以实现选择性极性翻转。测得的接近零的哈米特ρ值与芳基噻蒽鎓盐向钯（0）的氧化加成对取代基效应不敏感一致，这使得该反应能够与结构和电子性质多样的芳基噻蒽鎓盐发生反应。此外，我们通过偶联两个否则难以一步合成的复杂片段，展示了该方法的稳健性。
