940-19-2Relevant academic research and scientific papers
Difluoro(aryl)(perfluoroalkyl)-λ4-sulfanes and Selanes: Missing Links of Trichloroisocyanuric Acid/Potassium Fluoride Chemistry
Brüning, Fabian,Pitts, Cody Ross,Kalim, Jorna,Bornemann, Dustin,Ghiazza, Clément,de Montmollin, Jean,Trapp, Nils,Billard, Thierry,Togni, Antonio
supporting information, p. 18937 - 18941 (2019/11/26)
The TCICA/KF approach to oxidative fluorination of heteroatoms has emerged as a surprisingly simple, safe, and versatile surrogate to classically challenging fluorination reactions. Although polyfluorination (or chlorofluorination) of diaryl disulfides, diaryl diselenides, diaryl ditellurides, aryl iodides, and aryl(perfluoroalkyl)tellanes has been described, the application of this TCICA/KF methodology to aryl(perfluoroalkyl)sulfanes and selanes remains an area of unexplored chemical space. Accordingly, to address the “missing links” in the developing series of chalcogen-based substrate reactivity, we report mild syntheses of metastable difluoro(aryl)(perfluoroalkyl)-λ4-sulfanes and selanes. As only limited examples of these species exist in the current literature (accessible only by using F2 or XeF2/HF), we have carried out detailed structural analyses, primarily using NMR and SC-XRD data. In addition, we investigate the effect of the perfluoroalkyl chain on the outcome of oxidative fluorination, and, finally, we provide preliminary evidence that difluoro(aryl)(trifluoro-methyl)-λ4-sulfanes may act as fluorinating reagents.
Metal-free trifluoromethylthiolation of arenediazonium salts with Me4NSCF3
Bertoli, Giulia,Exner, Benjamin,Evers, Mathies V.,Tschulik, Kristina,Goo?en, Lukas J.
, p. 132 - 136 (2018/04/05)
A metal-free entry to the pharmaceutically meaningful substrate class of trifluoromethyl thioethers has been developed starting from widely available arenediazonium salts and commercially available Me4N+SCF3?. This reaction proceeds within one hour at 0 °C and is applicable to a wide range of functionalized substrates.
Iron-Catalyzed Decarboxylation of Trifluoroacetate and Its Application to the Synthesis of Trifluoromethyl Thioethers
Exner, Benjamin,Bayarmagnai, Bilguun,Jia, Fan,Goossen, Lukas J.
supporting information, p. 17220 - 17223 (2016/01/25)
Nucleophilic CF3 has been generated by decarboxylation of potassium trifluoroacetate, arguably the most easy-to-handle, inexpensive, and sustainable source of trifluoromethyl groups. Simple iron(II) chloride catalyzes the decarboxylation as well as a subsequent trifluoromethylation of organothiocyanates, resulting in a straightforward synthesis of trifluoromethyl thioethers. The KCN byproduct is absorbed by iron(II) with formation of nontoxic potassium hexacyanoferrate. An analogous trifluoromethylation of aldehydes with trifluoroacetate underlines the synthetic potential of such iron-catalyzed decarboxylative trifluoromethylations.
Electronic nature of perfluoroalkylthio-, perfluoroalkylseleno-, and perfluoroalkyltelluro-containing substituents
Kondratenko, N. V.,Popov, V. I.,Kolomeitsev, A. A.,Saenko, E. P.,Prezhdo, V. V.,et al.
, p. 1049 - 1054 (2007/10/02)
The ? constants of perfluoroalkylthio, perfluoroalkylseleno, perfluoroalkyltelluro, and perfluoroalkylsulfonyl groups were determined by the 19F NMR method.It was shown that the perfluoro-tert-butylsulfonyl group is the most electron-withdrawing of all the known stable substituents.The dipole moments of aryl perfluoroalkyl sulfides and sulfones were determined.
