Regiodivergent aromatic electrophilic substitution using nitrosoarenes in hexafluoroisopropanol: a gateway for diarylamines and p-iminoquinones synthesis

Abstract

A metal-free aromatic electrophilic substitution reaction using nitrosoarenes as the electrophile in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) is reported. HFIP activates nitrosoarene towards the electrophilic C- H amination followed by a concomitant Nð€€€ O bond cleavage to deliver diarylamines without requiring any extra reagent or further treatment. The dual electrophilic nature of nitrosoarene permits a switchover of selectivity to Cð€€€ H oxygenation furnishing dearomatizedp-iminoquinones following a unique mechanistic rationale of two consecutive [2,3] sigmatropic rearrangement in nitroso-chemistry.