Visible Light-Promoted Metal-Free C–H Activation: Diarylketone-Catalyzed Selective Benzylic Mono- and Difluorination

We report herein an operationally simple method for the direct conversion of benzylic C-H groups to C-F. We show that visible light can activate diarylketones to abstract a benzylic hydrogen atom selectively. Adding a fluorine radical donor yields the benzylic fluoride and regenerates the catalyst. The selective formation of mono- and difluorination products can be achieved by catalyst control. 9-Fluorenone catalyzes benzylic C-H monofluorination, while xanthone catalyzes benzylic C-H difluorination. The scope and efficiency of this new C-H fluorination method are significantly better than those of the existing methods. This is also the first report of selective C-H gem-difluorination.

• WF
  Welch Foundation

  Award: I-1596
• NI
  National Institutes of Health

  Award: R01-GM079554
• NI
  National Institute of General Medical Sciences