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).
Angew Chem Int Ed Engl. 2014 Dec 22;53(52):14559-63. doi: 10.1002/anie.201409375. Epub 2014 Oct 30.
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 NOCF3 bond followed by recombination of the resulting nitrenium ion and trifluoromethoxide is proposed for the OCF3 -migration reaction.
通过两步序列的 O-三氟甲基化 N-芳基-N-羟胺衍生物和分子内 OCF3 迁移，实现了芳基三氟甲氧基化。该方案可轻松获得广泛的合成有用的邻位-OCF3 苯胺衍生物。此外，它还利用了稳定的试剂，操作简单，具有高官能团容忍度，适用于克级规模以及一锅合成。对于 OCF3 迁移反应，提出了 NOCF3 键的异裂裂解以及随后生成的氮翁离子和三氟甲氧基的重组的反应机理。
