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.

Graphical abstractA 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 full-size imageDownload 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.