Photoinduced benzylic C–H thiocyanation enabled by triphenylphosphine oxide and <i>N</i> -thiocyanophthalimide

Herein, we report a mild, photoinduced benzylic C<b>-</b>H thiocyanation mediated by an electron donor-acceptor complex between triphenylphosphine oxide and <i>N</i>-thiocyanophthalimide. Utilizing triphenylphosphine oxide as the pivotal catalyst, this metal- and photocatalyst-free method affords benzyl thiocyanates under ambient conditions with broad substrate scope and excellent functional group tolerance, enabling late-stage diversification.