Oxidative desulfurization-fluorination

The oxidative desulfurization-fluorination of methyl A,-alkyl-A,-pyridyl(or pyrimidin-yl)dilhiocarbamates produces the corresponding (trifluoromethyl)amino-substituted pyridines (or pyrimidines) 5.69... 

Oxidative Desulfurization-Fluorination of Methyl A - Alkyl- V-heteryldithiocarbamates General Procedure 49... 

Hiyama [22] et al. developed the oxidative desulfurization-fluorination of dithio-carbonates (xanthogenates) by treatment with l,3-dibromo-5,5-dimethylhydantoin (DBH) or N-bromosuccinimide (NBS) and a huge excess of 70 % hydrogen fluoride-pyridine (Olah s reagent, up to 80 equivalents). The corresponding trifluoromethyl ethers are formed in moderate to excellent yields. 

Kuroboshi M, Suzuki K, Hiyama T (1992) Oxidative desulfurization-fluorination of xanthates. A convenient synthesis of trifluoromethyl ethers and difluoro(methylthio)methyl ethers. Tetrahedron Lett 33 4173 176. doi 10.1016/S0040-4039(00)74681-8... 

Tetrabutylammonium dihydrogen trifluoride also performs oxidative desulfurization fluorina-tion of 2-substituted l,l,l-txis(methylsulfanyl)ethanes in the presence of DBH leading to a new route to partially fluorinated alkenes. l,l,l-tris(methylsulfanyl)-5-phenylpentane (22) reacts with TBADTF in the presence of DBH to give the fluoro derivative 23, which is converted to the fluoroalkene 25 via the sulfoxide 24 followed by pyrolysis.217... 

A review of the scope and limitations of fluoro-Pummerer rearrangements, oxidative desulfiirization-fluorination, and oxidative desulfurization-di- and tri-fluorination reactions for the synthesis of fluorinated compounds has been reported. ... 

Ar—O—CF3 and Ar—O—CHF2 type compounds are now accessible through the desulfurization-oxidative fluorination of dithiocarbonates and dithiianes. ° Introduction of a O—CHF2 group can also be performed by adding the corresponding difluorocarbene onto the phenolic hydroxyl (cf. Chapter 2). ° ... 

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