Ag-Mediated Reactions: Coupling and Heterocyclization Reactions

Weibel, Jean‐Marc; Blanc, Aurélien; Pale, Patrick

doi:10.1021/cr078365q

Cited by 429 publications

(149 citation statements)

References 188 publications

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“…Silver holds the most unexplored chemistry among the coinage metals and its redox chemistry is the least understood [1][2][3][4][5] . Ag(I) salts are commonly employed in organic transformations by exploiting three main properties (Fig.…”

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confidence: 99%

“…1). First, its moderate Lewis acidity has found application in activating allenes and alkynes to promote a nucleophilic attack over the unsaturation to render, for instance, the cyclization of allenols, allenones and allenoic acids 4,5 . The p-activation of terminal acetylenes can also produce silver(I)-acetylides 6,7 , which are known as efficient transmetallating agents and have been widely utilized in organopalladium catalysis [8][9][10] .…”

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confidence: 99%

“…The second important characteristic of Ag(I) chemistry is the insolubility of its corresponding halide salts (halogenophilicity). A large number of transition metal-catalysed reactions are conducted in the presence of Ag(I) salts to trigger the precipitation of AgX salts (X ¼ Cl, Br, I) from coordinatively saturated metal centres, for instance, in Pd-catalysed crosscoupling reactions involving aryl or alkenyl halides 5 , or in Au-catalysed C-C bond-forming reactions 11 . Finally, Ag(I) salts are extensively used as one-electron oxidant, for instance in the preparation of carbonyls from the corresponding alcohols under mild conditions 2,12 .…”

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Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis

et al. 2014

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Silver is extensively used in homogeneous catalysis for organic synthesis owing to its Lewis acidity, and as a powerful one-electron oxidant. However, two-electron redox catalytic cycles, which are most common in noble metal organometallic reactivity, have never been considered. Here we show that a Ag(I)/Ag(III) catalytic cycle is operative in model C–O and C–C cross-coupling reactions. An aryl-Ag(III) species is unequivocally identified as an intermediate in the catalytic cycle and we provide direct evidence of aryl halide oxidative addition and C–N, C–O, C–S, C–C and C–halide bond-forming reductive elimination steps at monometallic silver centres. We anticipate our study as the starting point for expanding Ag(I)/ Ag(III) redox chemistry into new methodologies for organic synthesis, resembling well-known copper or palladium cross-coupling catalysis. Furthermore, findings described herein provide unique fundamental mechanistic understanding on Ag-catalysed cross-coupling reactions and dismiss the generally accepted conception that silver redox chemistry can only arise from one-electron processesThis work was supported by grants from the European Research Council (Starting Grant Project ERC-2011-StG-277801), the Spanish MINECO (CTQ2012-37420-C02-01/BQU, CTQ2012-32436, Consolider-Ingenio CSD2010-00065, INNPLANTA project INP-2011-0059-PCT-420000-ACT1) and the Catalan DIUE of the Generalitat de Catalunya (2009SGR637

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Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis

et al. 2014

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“…The stronger base sodium hydroxide in ethanol/n-butanol at 90-100°C for 24 h, however, gave 4a (R = Ph) in 29% yield, whereas utilization of Pd(0)-catalyzed coupling with the milder base potassium fluoride in the presence of silver(I) oxide [23][24][25] in 2-methoxyethanol with THF to aid solubility gave 4a in an excellent yield (96%). Similarly, were the most red shifted and also had the smallest energy band gap.…”

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Rearrangement of Cyclotriveratrylene (CTV) Diketone: 9,10-Diarylanthracenes with OLED Applications

et al. 2012

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Electroluminescent 9,10-diaryl anthracenes have been shown to be promising host and hole-transporting materials in organic electroluminescence due to their high thermal stability, electrochemical reversibility and wide band gap useful for organic light emitting diodes (OLEDs), especially blue OLEDs. Oxidation of cyclotriveratrylene (CTV) to the corresponding diketone and subsequent bromination resulted in an unexpected rearrangement to a highly functionalized 9-aryl-10-bromoanthracene derivative, which was employed in Suzuki couplings to synthesize a series of 9,10-diaryl compounds that are structural analogs of anthracene derivatives used in the preparation of OLEDs, but are more highly functionalized, including electron-donating methoxy groups in addition to substitution by a carboxylic acid moiety. The UV/fluorescence solution spectra show strong emissions at a 446 nm, 438 nm and 479 nm, respectively, for the anthracene 10-phenyl, 10-naphthyl and 10-pyrenyl adducts containing a benzoic acid functional group, whereas the analogs bearing the hydroxymethylene moiety from reduction of the benzoic acid to the corresponding alcohols gave much shorter emission wavelengths of 408 nm, 417 nm, and 476 nm, respectively, and had somewhat higher quantum yields, suggesting they are better candidates for OLED applications.

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“…[11] And we believe that the AgSbF 6 behaves as a s-Lewis acid in such a case. [12] The nucleophilic attack between isocyanide 1 and the vinyl-cation B essentially leads to the formation of zwitterionic species, which exist as a resonance-stablized intermediate C$D. [13] The intermediate experiences further Michael addition followed by intramolecular annulation to yield the product 4.…”

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Silver Hexafluoroantimonate‐Catalyzed Three‐Component [2+2+1] Cycloadditions of Allenoates, Dual Activated Olefins, and Isocyanides

Liu

et al. 2011

Adv Synth Catal

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The intermolecular [2 + 2 + 1] multicomponent cycloadditions from readily available allen-A C H T U N G T R E N N U N G oates, dual activated olefins and isocyanides catalyzed by silver hexafluoroantimonate were studied. This protocol allowed the syntheses of highly functionalized five-membered carbocycles with exclusive regioselectivity and stereoselectivity in an efficient and atom-economical manner.

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Ag-Mediated Reactions: Coupling and Heterocyclization Reactions

Cited by 429 publications

References 188 publications

Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis

Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis

Rearrangement of Cyclotriveratrylene (CTV) Diketone: 9,10-Diarylanthracenes with OLED Applications

Silver Hexafluoroantimonate‐Catalyzed Three‐Component [2+2+1] Cycloadditions of Allenoates, Dual Activated Olefins, and Isocyanides

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