[(tBu2PhP)Ag(μ-OCF3)]2: A Thermally Stable, Light-Insensitive Nucleophilic Reagent for Trifluoromethoxylation

Many trifluoromethoxylation approaches often proposed nucleophilic AgIOCF3 as a key intermediate. However, the structure of this intermediate remains elusive. Herein, the thermally stable, light-insensitive nucleophilic trifluoromethoxylating reagent [Ag(PPhtBu2)(OCF3)] (1) was prepared and fully characterized. Reagent 1 reacted with a variety of alkyl electrophiles including benzyl bromodes/chlorides, primary alkyl bromides/iodides/triflates/nosylates, and secondary alkyl bromides/triflates/nosylates in good to excellent yields. Mechanistic investigation by reaction with three enantioenriched secondary alkyl electrophiles suggested that these reactions proceed via an SN2 pathway, which is consistent with our original mechanistic hypothesis.