19031-63-1Relevant articles and documents
Mechanistic study of silver-catalyzed decarboxylative fluorination
Patel, Niki R.,Flowers, Robert A.
, p. 5834 - 5841 (2015)
The silver-catalyzed fluorination of aliphatic carboxylic acids by Selectfluor in acetone/water provides access to fluorinated compounds under mild and straightforward reaction conditions. Although this reaction provides efficient access to fluorinated alkanes from a pool of starting materials that are ubiquitous in nature, little is known about the details of the reaction mechanism. We report spectroscopic and kinetic studies on the role of the individual reaction components in decarboxylative fluorination. The studies presented herein provide evidence that Ag(II) is the intermediate oxidant in the reaction. In the rate-limiting step of the reaction, Ag(I)-carboxylate is oxidized to Ag(II) by Selectfluor. Substrate inhibition of the process occurs through the formation of a silver-carboxylate. Water is critical for solubilizing reaction components and ligates to Ag(I) under the reaction conditions. The use of donor ligands on Ag(I) provides evidence of oxidation to Ag(II) by Selectfluor. The use of sodium persulfate as an additive in the reaction as well as NFSI as a fluorine source further supports the generation of a Ag(II) intermediate; this data will enable the development of a more efficient set of reaction conditions for the fluorination.
Preparation method of fluoride and intermediate thereof (by machine translation)
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Paragraph 0206-0208; 0228-0234, (2020/12/30)
The invention discloses a preparation method of fluoride and an intermediate thereof. The preparation method comprises the following steps: in the presence of a basic reagent, the compound III and the thionyl fluoride are reacted in an organic solvent to obtain the compound of the formula I. The preparation method can obtain the fluorosulfite compound in a high yield, and has good functional group compatibility and substrate universality. (by machine translation)
Discovery of 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride as a deoxofluorinating agent with high thermal stability as well as unusual resistance to aqueous hydrolysis, and its diverse fluorination capabilities including deoxofluoro-arylsulfinylation with high stereoselectivity
Umemoto, Teruo,Singh, Rajendra P.,Xu, Yong,Saito, Norimichi
supporting information; experimental part, p. 18199 - 18205 (2011/03/18)
Versatile, safe, shelf-stable, and easy-to-handle fluorinating agents are strongly desired in both academic and industrial arenas, since fluorinated compounds have attracted considerable interest in many areas, such as drug discovery, due to the unique effects of fluorine atoms when incorporated into molecules. This article describes the synthesis, properties, and reactivity of many substituted and thermally stable phenylsulfur trifluorides, in particular, 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride (Fluolead, 1k), as a crystalline solid having surprisingly high stability on contact with water and superior utility as a deoxofluorinating agent compared to current reagents, such as DAST and its analogues. The roles of substiuents on 1k in thermal and hydrolytic stability, fluorination reactivity, and the high-yield fluorination mechanism it undergoes have been clarified. In addition to fluorinations of alcohols, aldehydes, and enolizable ketones, 1k smoothly converts non-enolizable carbonyls to CF2 groups, and carboxylic groups to CF3 groups, in high yields. 1k also converts C(=S) and CH3SC(=S)O groups to CF2 and CF3O groups, respectively, in high yields. In addition, 1k effects highly stereoselective deoxofluoro-arylsulfinylation of diols and amino alcohols to give fluoroalkyl arylsulfinates and arylsulfinamides, with complete inversion of configuration at fluorine and the simultaneous, selective formation of one conformational isomer at the sulfoxide sulfur atom. Considering the unique and diverse properties, relative safety, and ease of handling of 1k in addition to its convenient synthesis, it is expected to find considerable use as a novel fluorinating agent in both academic and industrial arenas.
