C-F Transformations of Benzotrifluorides by the Activation of Ortho-Hydrosilyl Group.

Single C-F transformations of aromatic trifluoromethyl compounds are challenging issues due to the strong C-F bond. We have recently developed selective methods for single C-F transformations such as allylation of o-hydrosilyl-substituted benzotrifluorides through the hydride abstraction with trityl cations. Single C-F thiolation and azidation of o-(hydrosilyl)benzotrifluorides were achieved using trityl sulfides and trityl azide catalyzed by Yb(OTf) 3 . Treatment of o-(hydrosilyl)benzotrifluorides with trityl chloride resulted in single C-F chlorination. The resulting fluorosilyl group served in further transformations including protonation, halogenation, and Hiyama cross-coupling with C-Si cleavage. We also synthesized benzyl fluorides by LiAlH 4 -reduction of the resulting fluorosilanes and further C-F transformations. These methods enabled us to prepare a broad range of organofluorines from simple benzotrifluorides through C-F and C-Si transformations.