Siladifluoromethylation and Deoxo-trifluoromethylation of PV-H Compounds with TMSCF3: Route to PV-CF2- Transfer Reagents and P-CF3 Compounds

Article abstract of DOI:10.1021/acs.orglett.9b00381

A method for siladifluoromethylation of dialkyl phosphonates and secondary phosphine oxides with TMSCF₃ to produce nucleophilic P^V-CF₂- transfer reagents is disclosed, with multigram 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 directing the chemoselectivity.