Decatungstate Catalyzed Benzylic C−H Trifluoromethylthiolation

Here we report a mild protocol for benzylic C−H trifluoromethylthiolation using sodium decatungstate (NaDT) as the photocatalyst. Wherein, photoactivated DT abstracted the benzylic hydrogen atom via a radical process. This transformation works well with a slight excess of benzylic substrates or as limiting reagents for better purification. The reaction shows mild conditions and good functional group tolerance. Moreover, the protocol could be applied to gram‐scale synthesis.