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

Autori
Capdevila, Lorena ; Andris, Erik ; Briš, Anamarija ; Tarrés, Màrius ; Roldán-Gómez, Steven ; Roithová, Jana ; Ribas, Xavi

Izvornik
ACS Catalysis (2155-5435) 8 (2018), 11; 10430-10436

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
silver ; cross-coupling ; two-electron redox catalysis ; mass spectrometry ; infrared photodissociation spectroscopy

Sažetak
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.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA