title: Trifluoromethoxylation of arenes: synthesis of ortho-trifluoromethoxylated aniline derivatives by OCF3 migration.
abstract: 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. A reaction 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.
authors.affiliation: Department of Chemistry, State University of New York at Stony Brook, Stony Brook, NY 11794-3400 (USA); Institute of Chemical Biology and Drug Discovery, State University of New York at Stony Brook, Stony Brook, NY 11794-3400 (USA).
authors.forename: Katarzyna N
authors.initials: KN
authors.lastname: Hojczyk
authors.forename: Pengju
authors.initials: P
authors.lastname: Feng
authors.forename: Chengbo
authors.initials: C
authors.lastname: Zhan
authors.forename: Ming-Yu
authors.initials: MY
authors.lastname: Ngai
mesh_terms: D000814:Aniline Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D005461:Fluorine / Q000737:chemistry; D019811:Hydroxylamine / Q000737:chemistry
chemical_list: D000814:Aniline Compounds; D005461:Fluorine; D019811:Hydroxylamine
keywords: amides; arenes; fluorine; rearrangement; synthetic methods