Hexafluoro‐2‐propanol Promotes para‐Selective C–H Amination of Free Anilines with Azodicarboxylates

An effective, mild, and clean method for the C–H amination of free anilines with azodicarboxylates in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) without the need for any additional catalysts or reagents was developed. The reaction was found to be highly regioselective and provided a series of p ‐aminophenylhydrazine derivatives in excellent yields. Moreover, compatibility with a free amino group makes this protocol an attractive strategy in synthetic chemistry.