First examples of stable polyfluorinated bis- and tris-(alkoxy)methyl cations

Fluorodesulfurization of Thionobenzodioxoles with Silver(I) Fluoride

“…These results support the intermediacy of oxocarbenium intermediates in the desulfurative fluorination with AgF. This observation is also consistent with results reported previously by us in the synthesis of difluoroethers from thionoesters using AgF, and the 19 F NMR chemical shift is consistent with reports of fluorinated oxocarbeniums by Petrov . It is noteworthy that the difluorobenzodioxoles depicted in Figure exhibit excellent stability compared to difluoroethers previously prepared by us …”

“…This observation is also consistent with results reported previously by us in the synthesis of difluoroethers from thionoesters using AgF, 18 and the 19 F NMR chemical shift is consistent with reports of fluorinated oxocarbeniums by Petrov. 22 It is noteworthy that the difluorobenzodioxoles depicted in Figure 2 exhibit excellent stability compared to difluoroethers previously prepared by us. 18 In summary, we report a mild method for the preparation of difluorobenzodioxoles from catechols using a sequence involving formation of a thionocarbonate, followed by reaction with AgF.…”