CF ₃ SO ₃ CF ₃ /DMAP‐Mediated Condensation of Carboxylic Acids With O

A CF ₃ SO ₃ CF ₃ /DMAP‐mediated esterification of carboxylic acids with alcohols and phenol is developed under mild conditions. The reaction avoided the use of strong acids or other harsh reagents and furnished the corresponding esters in excellent yields, showing good functional group tolerance and a wide range of substrates. The protocol was also applicable to amines, thiols, and complex molecules, offering a promising strategy for the convenient synthesis of prodrugs. Mechanistically, CF ₃ SO ₃ CF ₃ functions as a dual condensation reagent in the reaction, where acyl fluoride and anhydride generated in situ from carboxylic acid and CF ₃ SO ₃ CF ₃ are proved to be key intermediates. This work has expanded the synthetic application of CF ₃ SO ₃ CF ₃ far beyond traditional trifluoromethoxylation.