Trifluoromethoxylation of arenes: Synthesis of ortho- Trifluoromethoxylated aniline derivatives by OCF3 migration

Article abstract of DOI:10.1002/anie.201409375

Aryl trifluoromethoxylation by a two-step sequence of O-trifluoromethylation of N-aryl-N-hydroxylamine derivatives and intramolecular OCF₃ migration is presented. This protocol allows easy access to a wide range of synthetically useful ortho-OCF₃ aniline derivatives. In addition, it utilizes bench-stable reagents, is operationally simple, shows high functional-group tolerance, and is amenable to gram-scale as well as one-pot synthesis.Areaction mechanism of a heterolytic cleavage of the N-OCF₃ bond followed by recombination of the resulting nitrenium ion and trifluoromethoxide is proposed for the OCF₃-migration reaction.