Silver-catalysed C–H bond activation: a recent review

Radhika, Sankaran; Abdulla, C. M. Afsina; Aneeja, Thaipparambil; Anilkumar, Gopinathan

doi:10.1039/d1nj02156g

Cited by 17 publications

(7 citation statements)

References 82 publications

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“…Halogenated (products 13 , 14 , and 17 ), cyano (product 15 ), methoxy (product 16 ), and ortho-disubstituted (product 18 ) aromatic compounds react with 5 in good to excellent yields and still in short reaction times (<2 h). These results should be remarked upon as this is difficult to find in the open literature Ag-catalyzed Buchner ring expansion reactions. − The slightly lower results obtained for the bigger substrates 11 and 12 can be explained by the size discrimination associated to the microporous structure of MOF 3 . To check this, 1,3,5-triisopropylbenzene 19 was tested as a substrate for the reaction, and product 20 was not found (Figure S17).…”

Section: Resultsmentioning

confidence: 87%

“…These results should be remarked upon as this is difficult to find in the open literature Ag-catalyzed Buchner ring expansion reactions. 32 − 35 The slightly lower results obtained for the bigger substrates 11 and 12 can be explained by the size discrimination associated to the microporous structure of MOF 3 . To check this, 1,3,5-triisopropylbenzene 19 was tested as a substrate for the reaction, and product 20 was not found ( Figure S17 ).…”

Section: Resultsmentioning

confidence: 88%

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Highly Efficient MOF-Driven Silver Subnanometer Clusters for the Catalytic Buchner Ring Expansion Reaction

et al. 2022

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The preparation of novel efficient catalysts—that could be applicable in industrially important chemical processes—has attracted great interest. Small subnanometer metal clusters can exhibit outstanding catalytic capabilities, and thus, research efforts have been devoted, recently, to synthesize novel catalysts bearing such active sites. Here, we report the gram-scale preparation of Ag 2 0 subnanometer clusters within the channels of a highly crystalline three-dimensional anionic metal–organic framework, with the formula [Ag 2 0 ]@Ag I 2 Na I 2 {Ni II 4 [Cu II 2 (Me 3 mpba) 2 ] 3 }·48H 2 O [Me 3 mpba 4– = N,N ′-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. The resulting crystalline solid catalyst—fully characterized with the help of single-crystal X-ray diffraction—exhibits high catalytic activity for the catalytic Buchner ring expansion reaction.

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Section: Resultsmentioning

confidence: 87%

Section: Resultsmentioning

confidence: 88%

Highly Efficient MOF-Driven Silver Subnanometer Clusters for the Catalytic Buchner Ring Expansion Reaction

et al. 2022

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“…They also highlighted another reaction mechanism in case of N-fluorobenzenesulfonimide (NFSI) as a fluorine source instead of selectfluor and sodium persulfate as an additive (Scheme 17). The use of these reagents also supports the formation of Ag(II) intermediate (40) in the reaction. The use of these reaction mechanisms helps in the development of a more efficient reaction conditions for the fluorination via silver catalyzed decarboxylative fluorination.…”

Section: Decarboxylative Fluorinationmentioning

confidence: 56%

“…Further in 2015, Flowers II and co-workers elaborate the mechanistic studies for the Ag(I) catalyzed decarboxylative fluorination using spectroscopic and kinetic, [71] and proposed different mechanisms (Scheme 16) to that reported previously. [69] The proposed reaction pathway shows the formation of Ag(II) intermediate (40) after oxidation by select-fluor instead of Ag(III) and this is also the rate limiting step in the reaction. This Ag(II) intermediate form CO2 and an alkyl radical by oxidizing the carboxylate ligand, later this alkyl radical abstract fluorine from selectfluor to form the fluorinated product (42).…”

Section: Decarboxylative Fluorinationmentioning

confidence: 99%

“…Silver being a late transition metal catalyst has been efficiently used to catalyze several reactions in the organic chemistry. [35][36][37][38][39][40][41][42] Initially, in fluorination reaction silver was used as a mediator, [43,44] later on it has been efficiently used to catalyze the CÀ F bond formation reactions [45] of prefunctionalized starting materials. [46] Nowadays, the silver catalyst has been efficiently used for the CÀ F and CÀ CF 3 bond activation reactions, which may be due to the formation of redox couple by silver, as compared to mononuclear complexes.…”

Section: Introductionmentioning

confidence: 99%

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Emergence of Ag as a Catalyst of Choice for Fluorination and Trifluoromethylation Reactions

2023

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Carbon‐fluorine bond being highly polar in nature, its presence in pharmaceutically active molecules has huge impact on their chemical and physical properties. However, fluorine being highly electronegative and small in size, limits its nucleophilicity to the large extent; hence the incorporation of fluorine in the organic molecules is not an easy task. Due to this, demand for a suitable catalyst for fluorination reaction has been raised, which lowers the activation energy of these reactions and makes C−F/CF3 bond formation reaction kinetically more feasible. Silver being a late transition metal catalyst has been efficiently used to catalyze several reactions in the organic chemistry and has the substantial potential to catalyze the fluorination reactions. This Review shows the silver catalyzed fluorination and trifluoromethylation reactions for the synthesis of F/CF3 containing aromatic, aliphatic and heterocyclic compounds. All the sections have been elaborated using general discussion of the method, exploration of substrate scope, insight into the mechanistic studies and the shortcomings of the methods. After reading this Review article the readers can develop a detailed understanding of concept of silver metal catalyzed fluorination and trifluoromethylation reactions which can be explored for synthesizing molecules of biological interest.

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Silberfreie C−H‐Aktivierung: Strategische Ansätze zur Erschließung des vollen Potenzials von C−H‐Aktivierungen in der nachhaltigen organischen Synthese

Mondal

Gemmeren

2022

Angewandte Chemie

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Die Aktivierung von C-H-Bindungen gilt als eine der attraktivsten Methoden in der organischen Synthesechemie, da sie das Potenzial hat, Synthesewege zu verkürzen und eine gegenüber herkömmlichen Synthesestrategien komplementäre Produktpalette zu erzeugen. Bei vielen aktuellen Methoden werden jedoch Silbersalze als Additive eingesetzt, was zu stöchiometrischem Metallabfall führt und so verhindert, dass das volle Potenzial der CÀ H-Aktivierung ausgeschöpft werden kann. Daher erhält die Entwicklung von silberfreien Protokollen in letzter Zeit immer mehr Aufmerksamkeit. Mechanistisch kann Silber bei der CÀ H-Aktivierung verschiedene Funktionen erfüllen, sodass die Vermeidung des Einsatzes von Silber unterschiedliche Ansätze erfordert, je nachdem, welche Funktion es in einem bestimmten Prozess erfüllt. In diesem Aufsatz wird ein Vergleich von silberbasierten und -freien Methoden vorgestellt. Wir konzentrieren uns auf die strategischen Ansätze zur Entwicklung einer silberfreien CÀ H-Aktivierung und statten den Leser mit dem nötigen Grundwissen aus, um nachhaltige Methoden für die CÀ H-Aktivierung zu entwickeln.

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Silver-catalysed C–H bond activation: a recent review

Abstract: Transition-metal catalysed C-H activations are efficient, simple, mild, cost-effective, stereo selective and many of them are environmentally sustainable transformations. These were the dominant reasons which consistently inspired scientists to explore...

Cited by 17 publications

References 82 publications

Highly Efficient MOF-Driven Silver Subnanometer Clusters for the Catalytic Buchner Ring Expansion Reaction

Highly Efficient MOF-Driven Silver Subnanometer Clusters for the Catalytic Buchner Ring Expansion Reaction

Emergence of Ag as a Catalyst of Choice for Fluorination and Trifluoromethylation Reactions

Silberfreie C−H‐Aktivierung: Strategische Ansätze zur Erschließung des vollen Potenzials von C−H‐Aktivierungen in der nachhaltigen organischen Synthese

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