title: Product Control in Alkene Trifluoromethylation: Hydrotrifluoromethylation, Vinylic Trifluoromethylation, and Iodotrifluoromethylation using Togni Reagent.
abstract: Hydrotrifluoromethylation, vinylic trifluoromethylation, and iodotrifluoromethylation of simple alkenes have been achieved by using Togni reagent in the absence of any transition metal catalyst. These reactions were readily controllable by selection of appropriate salts and solvents. The addition of K2CO3 afforded the hydrotrifluoromethylation product, with DMF acting not only as a solvent, but also as the hydrogen source. In contrast, the use of tetra-n-butylammonium iodide (TBAI) in 1,4-dioxane resulted in vinylic trifluoromethylation, while the use of KI afforded the iodotrifluoromethylation product. The vinylic trifluoromethylation product was obtained by treatment of the iodotrifluoromethylation product with ammonium 2-iodobenzoate, indicating that it was formed through an elimination reaction of the in-situ-generated iodotrifluoromethylation product, and the solubility of the resulting 2-iodobenzoate salt plays a key role in the product switching. A radical-clock experiment showed that these reactions proceed via radical intermediates.
authors.affiliation: Synthetic Organic Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.|Sodeoka Live Cell Chemistry Project, ERATO, Japan Science and Technology Agency, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.|School of Pharmaceutical Sciences, University of Shizuoka, 5-1 Yada, Suruga-ku, Shizuoka, 422-8526, Japan.
authors.forename: Hiromichi
authors.initials: H
authors.lastname: Egami
authors.affiliation: Synthetic Organic Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.|Graduate School of Science and Engineering, Saitama University, 255 Shimo-okubo, Sakura-ku, Saitama, 338-8570, Japan.
authors.forename: Yoshihiko
authors.initials: Y
authors.lastname: Usui
authors.affiliation: Synthetic Organic Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.|Sodeoka Live Cell Chemistry Project, ERATO, Japan Science and Technology Agency, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.|RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
authors.forename: Shintaro
authors.initials: S
authors.lastname: Kawamura
authors.affiliation: Graduate School of Science and Engineering, Saitama University, 255 Shimo-okubo, Sakura-ku, Saitama, 338-8570, Japan.
authors.forename: Sayoko
authors.initials: S
authors.lastname: Nagashima
authors.affiliation: Synthetic Organic Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan. sodeoka@riken.jp.|Sodeoka Live Cell Chemistry Project, ERATO, Japan Science and Technology Agency, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan. sodeoka@riken.jp.|Graduate School of Science and Engineering, Saitama University, 255 Shimo-okubo, Sakura-ku, Saitama, 338-8570, Japan. sodeoka@riken.jp.|RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan. sodeoka@riken.jp.
authors.forename: Mikiko
authors.initials: M
authors.lastname: Sodeoka
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry; D006846:Hydrocarbons, Halogenated; D008745:Methylation; D015394:Molecular Structure; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D000475:Alkenes; D006845:Hydrocarbons, Fluorinated; D006846:Hydrocarbons, Halogenated; D014753:Vinyl Compounds; C105057:trifluoroiodomethane
keywords: Togni reagent; additive effect; alkenes; difunctionalization; trifluoromethylation