Tertiary‐Amine‐Initiated Synthesis of Acyl Fluorides from Carboxylic Acids and CF3SO2OCF3

A convenient method for deoxyfluorination of aromatic and aliphatic carboxylic acids with CF3SO2OCF3 in the presence of a suitable base at room temperature has been developed. The reaction allows a straightforward access to a variety of acyl fluorides and proves that CF3SO2OCF3 is an effective deoxyfluorination reagent for carboxylic acids. The method features simplicity, expeditiousness, high efficiency, ease of handling, good functional group tolerance, a wide range of substrates, excellent yields of products, compatibility of many amine initiators, use of environmentally friendly reagents, and effortless removal of byproducts. This reaction represents the first utilization of trifluoromethyl trifluoromethanesulfonate as a fluorination reagent. Amine‐triggered deoxyfluorination of carboxylic acids with CF3SO2OCF3 is described. The reaction proceeds rapidly at room temperature under metal‐free conditions to form various acyl fluorides in up to 97 % yield. This protocol represents the first utilization of trifluoromethyl trifluoromethanesulfonate as a convenient and efficient fluorination reagent.