High-Valent Cu, Ag, and Au Coordination Compounds

Ribas, Xavi; Capdevila, Lorena; Font, Pau

doi:10.1016/b978-0-08-102688-5.00106-9

Cited by 3 publications

(4 citation statements)

References 228 publications

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“…step were provided by Latos‐Grazyński and co‐workers [23] . To meet success, the authors used carbaporphyrinoids to encapsulate the Ag III thus ensuring the square planarity of the resulting macrocyclic aryl‐Ag III platform 1 , a key feature in the stabilization of highly oxidized silver [24] . With 1 in hand, they studied the pyridination of the aromatic ring (Figure 4 top), [23a] as well as other aryl‐N, aryl‐O and aryl‐P bond formations [23b–e] .…”

Section: Cross‐coupling Enabled By Agi/agiii Redox Sequencesmentioning

confidence: 99%

“…[23] To meet success, the authors used carbaporphyrinoids to encapsulate the Ag III thus ensuring the square planarity of the resulting macrocyclic aryl-Ag III platform 1, a key feature in the stabilization of highly oxidized silver. [24] With 1 in hand, they studied the pyridination of the aromatic ring (Figure 4 top), [23a] as well as other aryl-N, aryl-O and aryl-P bond formations. [23b-e] While the presence of Ag III intermediates was initially inferred on the basis of the achieved regioselectivity and the known stabilization of Ag III by corroles and carbaporphyrinoids, [25] the authors synthesized different aryl-Ag III complexes (2-3) at a later stage, [26] and proved unequivocally their ability to build aryl-N and aryl-P bonds with yields ranging from 45 % to 95 % (Figure 4 bottom).…”

Section: Pioneering C(sp 2 )à C and C(sp 2 )-Heteroatom Couplings Med...mentioning

confidence: 99%

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Cross‐Coupling Reactions Enabled by Well‐Defined Ag(III) Compounds: Main Focus on Aromatic Fluorination and Trifluoromethylation

Demonti

Joven-Sancho

Nebra

2023

The Chemical Record

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AgIII compounds are considered strong oxidizers of difficult handling. Accordingly, the involvement of Ag catalysts in cross‐coupling via 2e− redox sequences is frequently discarded. Nevertheless, organosilver(III) compounds have been authenticated using tetradentate macrocycles or perfluorinated groups as supporting ligands, and since 2014, first examples of cross‐coupling enabled by AgI/AgIII redox cycles saw light. This review collects the most relevant contributions to this field, with main focus on aromatic fluorination/perfluoroalkylation and the identification of AgIII key intermediates. Pertinent comparison between the activity of AgIIIRF compounds in aryl‐F and aryl‐CF3 couplings vs. the one shown by its CuIIIRF and AuIIIRF congeners is herein disclosed, thus providing a more profound picture on the scope of these transformations and the pathways commonly associated to C−RF bond formations enabled by coinage metals.

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Section: Cross‐coupling Enabled By Agi/agiii Redox Sequencesmentioning

confidence: 99%

Section: Pioneering C(sp 2 )à C and C(sp 2 )-Heteroatom Couplings Med...mentioning

confidence: 99%

Cross‐Coupling Reactions Enabled by Well‐Defined Ag(III) Compounds: Main Focus on Aromatic Fluorination and Trifluoromethylation

Demonti

Joven-Sancho

Nebra

2023

The Chemical Record

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“…[149] is an example of Ag(III) chemistry that in opposite to copper and gold, remains scarcely explored in cross-coupling. [150] Pioneering work by Ritter, Li, Hartwig and Sarpong allowed for the fluorination of distinct skeletons and pointed to the capital role of elusive Ag(II)-F or Ag(III)-F compounds. [151][152][153][154][155][156][157][158] Organosilver(III) salts enabling trifluoromethylation were reported recently by Menjon: [(Ph) 4 P][Ag(CF 3 ) 3 F] [159] and Shen: [(Bu) 4 N][Ag(CF 3 ) 3 Ar] (Ar = aryl).…”

Section: Direct Formation Of C(sp 2 )à C(sp 3 ) Bondmentioning

confidence: 99%

“…New trifluoromethylation protocol affords a wide range of trifluoromethylated aromatic and heteroaromatic systems with very good yields. Nebra group protocol of trifluoromethylation is an example of Ag(III) chemistry that in opposite to copper and gold, remains scarcely explored in cross‐coupling [150] . Pioneering work by Ritter, Li, Hartwig and Sarpong allowed for the fluorination of distinct skeletons and pointed to the capital role of elusive Ag(II)‐F or Ag(III)‐F compounds [151–158] .…”

Section: Silver In C−h Bond Functionalizationmentioning

confidence: 99%

Application of Silver Compounds in Fluoroorganic Synthesis: A Minireview

2023

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The mini‐review is focused on application of silver and its compounds in fluoroorganic synthesis, and it reflects immense progress in this field which took place during the last two decades, with additional examples of reactivity of historical importance. Reactions of C−H, C−F, N−H and O−H bond functionalization, as well as catalysis of cycloaddition reactions and intramolecular rearrangement, retro‐rearrangement, and functional group migrations, have been described. Whenever available in original works, the reaction mechanisms were discussed. Since silver may be catalytically active in each of its available oxidation states from (0), via (I) and (II) to (III) with their immensely diverse properties, the organofluorine part is preceded by a brief overview of chemistry of silver in general. Uniqueness of silver among Group 11 elements is highlighted.

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Cross‐Coupling through Ag(I)/Ag(III) Redox Manifold

Demonti

Saffon‐Merceron

Mézailles

et al. 2021

Chemistry A European J

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In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e À redox steps. Definite proof is herein provided for the required elementary steps to accomplish the oxidative trifluoromethylation of arenes through Ag I /Ag III redox catalysis (i. e. CEL coupling), namely: i) easy Ag I /Ag III 2e À oxidation mediated by air; ii) bpy/phen ligation to Ag III ; iii) boron-to-Ag III aryl transfer; and iv) ulterior reductive elimination of benzotrifluorides from an [aryl-Ag III -CF 3 ] fragment. More precisely, an ultimate entry and full characterization of organosilver(III) compounds [K] + [Ag III (CF 3 ) 4 ] À (K-1), [(bpy)Ag III (CF 3 ) 3 ] (2) and [(phen)Ag III (CF 3 ) 3 ] (3), is described. The utility of 3 in crosscoupling has been showcased unambiguously, and a large variety of arylboron compounds was trifluoromethylated via [Ag III (aryl)(CF 3 ) 3 ] À intermediates. This work breaks with old stereotypes and misconceptions regarding the inability of Ag to undergo cross-coupling by itself.

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High-Valent Cu, Ag, and Au Coordination Compounds

Cited by 3 publications

References 228 publications

Cross‐Coupling Reactions Enabled by Well‐Defined Ag(III) Compounds: Main Focus on Aromatic Fluorination and Trifluoromethylation

Cross‐Coupling Reactions Enabled by Well‐Defined Ag(III) Compounds: Main Focus on Aromatic Fluorination and Trifluoromethylation

Application of Silver Compounds in Fluoroorganic Synthesis: A Minireview

Cross‐Coupling through Ag(I)/Ag(III) Redox Manifold

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