Defluorinative Hydrophosphorylation of Trifluoromethylated Enones: Insight into the Roles of H-Phosphine Oxide

The role of H-phosphoryl compounds in the conversion of the C-F bond has remained less explored. Here, an unprecedented sequence of defluorophosphorylation, defluorocyclization, and hydrodefluorination of trifluoromethylated enones with H-phosphoryl compounds is developed for the modular synthesis of structurally valuable multisubstituted furans. The streamlined strategy integrates new C-P(O) bond formation with multiple C(sp³)-F bond cleavage using multipurpose HP(O)R'R″ as both defluorinative surrogates and nucleophilic phosphorylating reagents. Moreover, water exhibits an unconventional hydrodefluorination reactivity in the presence of phosphoryl anions. Mechanistic studies support the dual roles of H-phosphoryl compounds in the defluorinative hydrophosphorylation of trifluoromethylated enones.