Fenton reagent-catalyzed trifluoromethylation of enamines of 3-oxocarboxylates with CF3I

• Published in: Journal of fluorine chemistry Vol. 181; pp. 1 - 6
• Main Authors: Ohtsuka, Yuhki, Uraguchi, Daisuke, Yamamoto, Kyoko, Tokuhisa, Kenji, Yamakawa, Tetsu
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 01.01.2016; Elsevier
• Subjects: (2,2,2-Trifluoroethyl)ketones; 3-Oxo-2-(trifluoromethyl)carboxylates; Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Fenton reagent; Physical Sciences; Science & Technology; Trifluoromethylation; 3-Oxo-2-(trifluoromethyl)carboxylates; Trifluoromethylation; (2,2,2-Trifluoroethyl)ketones; Fenton reagent; ALPHA-TRIFLUOROMETHYLATION; KETONE; EFFICIENT GENERATION; CARBONYL-COMPOUNDS; ACETALS; ALDEHYDES; ALDOL REACTION; SILYL ENOL ETHERS; RADICAL TRIFLUOROMETHYLATION; DERIVATIVES
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/j.jfluchem.2015.10.013

Fenton reagent-catalyzed trifluoromethylation of enamines of ethyl 3-oxocarboxylates with CF3I followed by acid hydrolysis provided 3-oxo-2-(trifluoromethyl)carboxylates in 64–94% yields, which converted (2,2,2-trifluoroethyl)ketones in satisfactory yields by hydrolysis and successive decarboxylation. •Trifluoromethylation of enamines of 3-oxocarboxylates proceeded smoothly with CF3I.•We improved of the yields of 3-oxo-2-(trifluoromethyl)carboxylates.•Hydrolysis and decarboxylation of the products by acid provided (2,2,2-trifluoroethyl)ketones. The trifluoromethylation of enamines of ethyl 3-oxocarboxylates catalyzed by Fenton reagent with CF3I was investigated. Trifluoromethylation followed by acid hydrolysis provided 3-oxo-2-(trifluoromethyl)carboxylates in 64–94% yields, which were greater than those obtained by the trifluoromethylation of 3-oxocarboxylates as reported previously. Enamines trifluoromethylated at the 2-position were isolated as intermediates. Hydrolysis and successive decarboxylation of the obtained 3-oxo-2-(trifluoromethyl)carboxylates under acidic conditions provided (2,2,2-trifluoroethyl)ketones in satisfactory yields.