Trifluoromethylthiolation of Hindered α-Bromoamides with Nucleophilic Trifluoromethylthiolating Reagents.

General methods have not been previously developed for the synthesis of sterically hindered α-SCF3-substituted carbonyl compounds using nucleophilic trifluoromethylthiolating reagents. Thus, we herein report sp3C-SCF3 bond formation in hindered α-bromoamides containing 3-bromo-oxindoles and linear α-bromoamides using CuSCF3 or AgSCF3 under mild conditions to access sterically hindered α-SCF3-substituted amides. This transformation is applicable to not only 3-SCF3-substituted oxindoles but also primary and secondary amides and reveals a broad functional group tolerance. This method will benefit the fields of medicinal and agricultural chemistry.

Ionic Liquid-Mediated Hydrofluorination of o-Azaxylylenes Derived from 3-Bromooxindoles.

The hydrofluorination reaction of 3-bromooxindole using mild HF reagents in an ionic liquid is described. This transformation can operate at room temperature to give a series of 3-substituted 3-fluorooxindole derivatives including racemic BMS 204352 (MaxiPost). The mechanistic study about interactions between HF and 3-butyl-1-methylimidazolium tetrafluoroborate [bmim][BF4] is also discussed on the basis of energy calculations.