A modular
synthetic method, involving a hydrothiolation, silylation,
and fluoroalkylation, for the construction of highly functionalized
fluoroalkyl sulfides has been developed. The use of aprotic polar
solvents enables the additive-free chemoselective hydrothiolation
of tetrafluoroethylene, trifluorochloroethylene, and hexafluoropropene
with various thiols. The stepwise functionalization reactions convert
the hydrothiolated intermediates into the tetrafluoroethyl sulfides
in high efficiency. The method avoids the use of the environmental
pollutant Halon-2402, which was employed as a building block in a
reported synthetic route.
A catalytic method for the synthesis of pentafluoroethyl ketones has been developed. The cesium fluoride catalyst can be used to convert acyl fluorides into the pentafluoroethyl ketones under tetrafluoroethylene pressure without generating stoichiometric quantities of chemical waste. Mechanistic studies suggest that high reaction temperature is crucial for the ketone to be the major product.
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