Reactivity of an electrophilic hypervalent iodine trifluoromethylation reagent with hydrogen phosphates—A mechanistic study

The electrophilic trifluoromethylation of hydrogen phosphates with the reagent trifluoromethyl-1,3-dihydro-3,3-dimethyl-1,2-benziodoxole (1) was studied by means of initial rates determined for pseudo first order setups and subsequent Taft analysis of the calculated relative rates. A positive polar sensitivity factor, indicative of a negative charge forming during the rate-determining step, was found for the whole data set.

A mechanistic study of the formation of trifluoromethyl phosphates by electrophilic trifluoromethylation of hydrogen phosphates is presented. The products easily decompose to corresponding fluorophosphates.Figure optionsDownload as PowerPoint slideHighlights
► The electrophilic trifluoromethylation of hydrogen phosphates is described.
► A mechanism is proposed based on kinetic data gathered by 19F NMR spectroscopy.
► Kinetic data have been analyzed by a modified Taft equation.