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Silver(I)-Catalyzed C–X, C–C, C–N, and C–O Cross-Couplings Using Aminoquinoline Directing Group via Elusive Aryl-Ag(III) Species

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journal contribution
posted on 01.10.2018, 00:00 by Lorena Capdevila, Erik Andris, Anamarija Briš, Màrius Tarrés, Steven Roldán-Gómez, Jana Roithová, Xavi Ribas
Cross-coupling transformations are a powerful tool in organic synthesis. It is known that this kind of transformation undergoes 2-electron redox processes, and, for this reason, silver has been nearly forgotten as catalyst for cross-couplings because silver is mainly considered as a 1-electron redox metal. Herein, we disclose effective Ag­(I)-catalyzed cross-coupling transformations using bidentate aminoquinoline as a directing group toward different nucleophiles to form C–C, C–N, and C–O bonds. DFT calculations indicate the feasible oxidative addition of L1-I substrate via the Ag­(I)/Ag­(III) catalytic cycle. Furthermore, ion spectroscopy experiments suggest a highly reactive aryl-Ag­(III) that in the absence of nucleophiles reacts to form an intermolecular cyclic product [5d-Ag­(I)-CH3CN], which in solution forms 5a. This work proves that silver can undergo 2-electron redox processes in cross-coupling reactions like Pd and Cu.