Product Control in Alkene Trifluoromethylation: Hydrotrifluoromethylation, Vinylic Trifluoromethylation, and Iodotrifluoromethylation using Togni Reagent

• Published in: Chemistry, an Asian journal an Asian journal, 2015-10, Vol.10 (10), p.2190-2199
• Main Authors: Egami, Hiromichi, Usui, Yoshihiko, Kawamura, Shintaro, Nagashima, Sayoko, Sodeoka, Mikiko
• Format: Article
• Language: English
• Subjects: additive effect; alkenes; Alkenes - chemistry; Chemistry; difunctionalization; Hydrocarbons, Fluorinated - chemistry; Hydrocarbons, Halogenated; Methylation; Molecular Structure; Togni reagent; trifluoromethylation; Vinyl Compounds - chemistry
• ISSN: 1861-4728; 1861-471X
• DOI: 10.1002/asia.201500359

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. Three for the price of one: Hydrotrifluoromethylation, vinylic trifluoromethylation, and iodotrifluoromethylation of simple alkenes have been selectively achieved by using Togni reagent in the absence of any transition metal catalyst with the appropriate salts and solvents.