Phosphadifluoromethylsilanes, by virtue of their mild activation conditions, have been extensively used in reactions with electrophiles and in cross-coupling. Their synthesis, however, utilizes toxic and corrosive reagents. Herein, we present a method for siladifluoromethylation of dialkyl phosphonates and secondary phosphine oxides with TMSCF3 to produce nucleophilic PV–CF2– transfer reagents, with multi-gram scale reactions included. Condition-dependent divergent reactivity under the established conditions is demonstrated by the formation of trifluoromethylphosphines. Both one-pot transformations are operationally simple and employ inexpensive materials. Mechanistic investigations suggest the divergent reactivity originates from a common intermediate, with Li+ concentration and electronics of the substituents directing the chemoselectivity.

Siladifluoromethylation and deoxo-trifluoromethylation of PV–H compounds with TMSCF3: Route to PV–CF2- transfer reagents and P–CF3 compounds

2019 Fall National Meeting

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