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Trifluoromethoxylation of Arenes: Synthesis of ortho ‐Trifluoromethoxylated Aniline Derivatives by OCF 3 Migration
Author(s) -
Hojczyk Katarzy.,
Feng Pengju,
Zhan Chengbo,
Ngai MingYu
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201409375
Subject(s) - chemistry , aniline , heterolysis , trifluoromethylation , hydroxylamine , intramolecular force , aryl , reagent , combinatorial chemistry , functional group , medicinal chemistry , stereochemistry , organic chemistry , catalysis , alkyl , polymer , trifluoromethyl
Aryl trifluoromethoxylation by a two‐step sequence of O‐trifluoromethylation of N‐aryl‐N‐hydroxylamine derivatives and intramolecular OCF 3 migration is presented. This protocol allows easy access to a wide range of synthetically useful ortho‐OCF 3 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 NOCF 3 bond followed by recombination of the resulting nitrenium ion and trifluoromethoxide is proposed for the OCF 3 ‐migration reaction.