2H-hexafluoroisopropylsilver

Polishchuk, V. R.; Fedorov, L. A.; Okulevich, P. O.; Герман, Л. С.; Knunyants, I. L.

doi:10.1016/s0040-4039(01)98628-9

Cited by 18 publications

(7 citation statements)

References 4 publications

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“…The yield of 4a was increased to 39% by increasing the amount of AgF to 4.0 equiv, and further screening of the solvents revealed that the transformation could also proceed in CH 3 CN, HMPA, and pyridine. It should be noted that although CH 3 CN was extensively used in the preparation of perfluoroalkylsilver metallic compounds, pyridine proved to be even better in this case, which might serve as both solvent and ligand for the organosilver intermediate (entry 7) . Apolar solvents like dioxane and toluene were inefficient owing to the insolubility of AgF in these solvents (entries 8 and 9).…”

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confidence: 99%

“…In our reaction, when 3.0 equiv of TEMPO (2,2,6,6-tetramethyl-1-oxylpiperidine) was added under standard reaction conditions with 3a as substrate, homocoupling was completely inhibited and 6 was isolated in 87% yield (Scheme ), which might support a free radical pathway. However, a concerted pathway could not be ruled out since, in pyridine, an aggregation state of perfluoroalkylsilver species has also been proposed based on NMR study …”

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confidence: 99%

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AgF-Mediated Fluorinative Homocoupling of gem-Difluoroalkenes

et al. 2013

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A novel silver(I)-fluoride-mediated homocoupling reaction of β,β-difluorostyrene derivatives is described. The transformation is initiated via nucleophilic addition of silver(I) fluoride to β,β-difluorostyrenes, which is followed by dimerization of the corresponding benzylsilver intermediates. The reaction shows good substrate scope, functional group tolerance, and represents the first report on the reactivity of (α-trifluoromethyl)benzylsilver species.

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confidence: 99%

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confidence: 99%

AgF-Mediated Fluorinative Homocoupling of gem-Difluoroalkenes

et al. 2013

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“…Optimum yields in the second reaction are obtained in refluxing pyridine, however. A similar preparation of AgCH(CF 3 ) 2 from (CF 3 ) 2 CHCO 2 Ag in pyridine is known, while the reactions between Hg(OAc) 2 and ArCO 2 H (Ar = (MeO) n C 6 H 5– n (OMe) n , n = 2 (2,6), 3 (2,3,4; 2,4,6)) in aqueous MeOH are reported to give HgAr 2 via Hg(OAc)Ar . The proposed mechanism for the latter reaction resembles that of electrophilic aromatic substitution.…”

Section: Introductionmentioning

confidence: 90%

Facile Decarboxylation of Propiolic Acid on a Ruthenium Center and Related Chemistry

et al. 2012

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Spontaneous decarboxylation of RCCCO 2 H (R = H, Ph) occurs in reactions with RuCl(PP)Cp (PP = (PPh 3 ) 2 , dppe) to give [Ru(CCHR)(PP)-Cp] + . Computational studies (DFT) of possible decarboxylation mechanisms suggest that the reaction that leads to extrusion of CO 2 and formation of [Ru(C CH 2 )(dppe)Cp] + most likely occurs by initial interaction of the anion HCCCO 2 − with RuCl(dppe)Cp by coordination of carboxylate to Ru, followed by formation of an η 2 -alkyne intermediate which rearranges to the η 1 -ethynyl species with loss of CO 2 . Protonation of the ethynyl group affords the parent vinylidene. In contrast, reactions of HCCCO 2 R (R = Me, Et) with RuCl(PP)Cp and [NH 4 ]PF 6 in MeOH have given [Ru{C(OMe)CH 2 (CO 2 R)}(PP)Cp] + , formed by attack of MeOH at C α of the intermediate vinylidenes [Ru{C CH(CO 2 R)}(PP)Cp] + . Deprotonation of the carbenes affords Ru{C(OMe)CH(CO 2 R)}(PP)Cp as mixtures of cis and trans isomers. The vinylidenes, which are obtained directly from RuCl(PP)Cp and HCCCO 2 R in the presence of [NH 4 ]PF 6 in Bu t OH, can be deprotonated (Na/Pr i OH) to the corresponding alkynyls. Attempted deprotonation of [Ru(C CH 2 )(dppe)Cp] + with LiBu gave the binuclear cyclobutenylidinium complex [{Ru(dppe)Cp} 2 (μ-C 4 H 3 )] + . The X-ray diffraction molecular structures of [{Ru(dppe)Cp} 2 (μ-C 4 H 3 )]PF 6 (11), [Ru{C(OMe)CH 2 (CO 2 Me)}(dppe)Cp]PF 6 (13), Ru{C-(OMe)CH(CO 2 R)}(dppe)Cp (R  Me (15), Et (16)) and Ru(CCCO 2 R)(dppe)Cp (R = Me (21), Et (22)) are described.

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“…In the next step, CF 2 CO 2 Et radical is generated by the oxidation of AgCF 2 CO 2 Et with PhI(OCOCF 3 )2. [151] Now the addition of this CF 2 CO 2 Et radical to alkyne generates vinyl radical (220), which undergoes hydrogen atom transfer and form alkyl radical intermediate (221). In the final step, fluorine atom transfer takes place from selectfluor to alkyl radical intermediate with the help of silver catalyst to form the final product (219).…”

Section: Chemcatchemmentioning

confidence: 99%

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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2H-hexafluoroisopropylsilver

Cited by 18 publications

References 4 publications

AgF-Mediated Fluorinative Homocoupling of gem-Difluoroalkenes

AgF-Mediated Fluorinative Homocoupling of gem-Difluoroalkenes

Facile Decarboxylation of Propiolic Acid on a Ruthenium Center and Related Chemistry

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

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