Gansäuer Andreas, von Laufenberg Daniel, Kube Christian, Dahmen Tobias, Michelmann Antonius, Behlendorf Maike, Sure Rebecca, Seddiqzai Meriam, Grimme Stefan, Sadasivam Dhandapani V, Fianu Godfred D, Flowers Robert A
Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, Gerhard Domagk Strasse 1, 53121 Bonn (Germany).
Chemistry. 2015 Jan 2;21(1):280-9. doi: 10.1002/chem.201404404. Epub 2014 Oct 28.
An atom-economical and catalytic arylation of epoxide-derived radicals is described. The key step of the catalytic system is a sequential electron and proton transfer for the rearomatization of the radical σ-complex and catalyst regeneration. Kinetic, computational, spectroscopic, and cyclovoltammetric investigations highlight the key issues of the reaction mechanism and catalyst stabilization by collidine hydrochloride. Studies employing radicophiles rule out the participation of cations as reactive intermediates.
本文描述了一种原子经济的、基于环氧化物衍生自由基的催化芳基化反应。该催化体系的关键步骤是通过连续的电子和质子转移实现自由基σ-络合物的再芳构化以及催化剂再生。动力学、计算、光谱和循环伏安法研究突出了反应机理的关键问题以及盐酸可力丁对催化剂的稳定作用。使用亲核试剂的研究排除了阳离子作为反应中间体的参与。
