Study of a Stable “Trifluoromethoxide Anion Solution” Arising from 2,4‐Dinitro‐Trifluoromethoxybenzene

• Published in: Chemistry : a European journal Vol. 27; no. 64; pp. 15986 - 15991
• Main Authors: Bonnefoy, Clémence, Chefdeville, Emmanuel, Panosian, Armen, Hanquet, Gilles, Leroux, Frédéric R., Toulgoat, Fabien, Billard, Thierry
• Format: Journal Article
• Language: English
• Published: Wiley-VCH Verlag 17.11.2021
• Subjects: 2,4-dinitro-trifluoromethoxybenzene; Chemical Sciences; Fluorine; Nucleophilic substitution; Organic chemistry; Trifluoromethoxide anion; Trifluoromethoxylation
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202102809

Despite recent advances, trifluoromethoxylation remains a challenging reaction. Here we describe an efficient trifluoromethoxylative substitution, using an inexpensive and easy‐to‐handle reagent. By mixing DMAP with a slight excess of 1,4‐dinitro‐trifluoromethoxybenzene (DNTFB), a stable solution of trifluoromethoxide anion is obtained and can be used to perform a SN2 reaction without any silver additives. A precise study of the properties and behavior of this unusual stable solution of CF3O− species is also performed. A stable solution of the trifluoromethoxide anion was readily obtained by mixing 2,4‐dinitro‐trifluoromethoxybenzene (DNTFB) and DMAP. A detailed study and characterization of this solution has been described, in particular highlighting the crucial role of the DNTFB/DMAP ratio. This “trifluoromethoxide anion solution” was applied to perform metal‐free SN2 reactions on alkyl bomides with yields up to 77 %.