Pengbo Zhang, Xinyi Guo, Mengke Yang, Longyu Wang, Yuzhen Gao
Direct phosphorothiolation of benzylic C(sp 3 )–H bonds remains underexplored. Herein, we report an energy transfer (EnT)-mediated method that achieves this via controlled radical–radical cross-coupling, using inexpensive K 2 S 2 O 8 as both an oxidant and a hydrogen atom transfer (HAT) reagent. This strategy eliminates prefunctionalization steps, demonstrates excellent chemoselectivity, and provides an atom- and step-economical route to diverse alkyl phosphorothioate compounds.