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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

Capdevila, Lorena; Andris, Erik; Briš, Anamarija; Tarrés, Màrius; Roldán-Gómez, Steven; Roithová, Jana; Ribas, Xavi (2018) Silver(I)-Catalyzed C–X, C–C, C–N, and C–O Cross-Couplings Using Aminoquinoline Directing Group via Elusive Aryl-Ag(III) Species. ACS Catalysis, 8 (11). pp. 10430-10436. ISSN 2155-5435

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Abstract

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.

Item Type: Article
Additional Information: This work was financially supported by grants from the European Research Council (Starting Grant Project ERC-2011-StG-277801 to X.R. and ERC-2015-CoG-682275 (IsoMS) to J.R), the Spanish MICINN (CTQ2016-77989-P to X.R), and the Catalan DIUE of the Generalitat de Catalunya (2017SGR264). X.R thanks ICREA for an ICREA Academia award. We thank COST Action CHAOS (CA15106) and STR from UdG for technical support.
Uncontrolled Keywords: silver; cross-coupling; two-electron redox catalysis; mass spectrometry; infrared photodissociation spectroscopy
Subjects: NATURAL SCIENCES > Chemistry
NATURAL SCIENCES > Chemistry > Organic Chemistry
Divisions: Division of Organic Chemistry and Biochemistry
Depositing User: Anamarija Briš
Date Deposited: 28 Nov 2019 14:17
Last Modified: 28 Nov 2019 14:17
URI: http://fulir.irb.hr/id/eprint/5162
DOI: 10.1021/acscatal.8b03257

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