Pd-catalyzed Suzuki–Miyaura cross-coupling of [Ph2SR][OTf] with arylboronic acids

• Published in: Tetrahedron Vol. 72; no. 47; pp. 7606 - 7612
• Main Authors: Wang, Xiao-Yan, Song, Hai-Xia, Wang, Shi-Meng, Yang, Jing, Qin, Hua-Li, Jiang, Xin, Zhang, Cheng-Pan
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 24.11.2016
• Subjects: Arylboronic acids; Fluorine; Palladium; Sulfonium salts; Palladium; Fluorine; Sulfonium salts; Arylboronic acids
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2016.10.018

The Pd-catalyzed Suzuki–Miyaura cross-coupling of alkyl- and fluoroalkyl(diphenyl)sulfonium triflates with arylboronic acids was compared. The fluorine substitution on the alkyl groups of [Ph2SR][OTf] had a big influence on the reaction. Perfluoroalkyl(diphenyl)sulfonium triflates (2b–d) were unsuccessful participants in the Pd-catalyzed phenylation of arylboronic acid under the standard conditions because of the strong electronegativity of the long-chain perfluoroalkyl groups, which underwent SRfn bond cleavage instead. Polyfluoroalkyl(diphenyl)sulfonium triflates (2f–h) reacted with arylboronic acid to afford the phenylation product in very low yields due to the tendency of deprotonation and β-F elimination of the sulfonium salts. Eventually, (2,2,2-trifluoroethyl)diphenylsulfonium triflate (2e), methyl- or ethyl(diphenyl)sulfonium triflate (2i or 2j), and triphenylsulfonium triflate (2m) were found to be more effective reagents than other tested phenylsulfounium salts for Pd-catalyzed phenylation, which provided much higher yields of the desired products under mild conditions. [Display omitted]