Copper-Catalyzed Oxidative Trifluoromethylation of Terminal Alkynes and Aryl Boronic Acids Using (Trifluoromethyl)trimethylsilane

• Published in: Journal of organic chemistry Vol. 77; no. 3; pp. 1251 - 1257
• Main Authors: Jiang, Xueliang, Chu, Lingling, Qing, Feng-Ling
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 03.02.2012; Amer Chemical Soc
• Subjects: Alkynes - chemistry; B derivatives; Boronic Acids - chemistry; Catalysis; Chemistry; Chemistry, Organic; Copper - chemistry; Exact sciences and technology; Hydrocarbons, Fluorinated - chemistry; Kinetics and mechanisms; Methylation; Noncondensed benzenic compounds; Organic chemistry; Organometalloidal and organometallic compounds; Oxidation-Reduction; Physical Sciences; Preparations and properties; Reactivity and mechanisms; Science & Technology; Silanes - chemistry; ROOM-TEMPERATURE; PALLADIUM; MEDIATED TRIFLUOROMETHYLATION; ARENES; CHEMISTRY; ORGANIC HALIDES; FLUORINATION; CU-II; REDUCTIVE ELIMINATION; BOND-FORMATION; Arene; Catalytic reaction; Acetylenic compound; Transition metal; Acetylene derivatives; Copper ion; Trifluoromethylation; Arylboronic acid; Reaction mechanism; Benzenic compound; Boron Organic compounds; Aromatic compound; Oxidation; Fluorine Organic compounds; Copper; Chemical synthesis; Boronic acid derivative; Boronic acids; Alkyne; Functional group
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo202566h

Trifluoromethylated acetylenes and arenes are widely applicable in the synthesis of pharmaceuticals and agrochemicals. In 2010, our group has reported the copper-mediated oxidative trifluomethylation of terminal alkynes and aryl boronic acids. This method allows a wide range of functional group tolerant trifluoromethylated acetylenes and arenes to be easily prepared. After the preliminary mechanistic studies of the oxidative trifluoromethylation of terminal alkyne, an efficient copper-catalyzed oxidative trifluoromethylation of terminal alkynes and aryl boronic acids has been developed. The catalytic protocol is successfully achieved by adding both the substrate and a portion of CF3TMS slowly using a syringe pump to the reaction mixture.