Qiong-Hui Peng, Ying-Li Cai, Hui Dai, Chunlin Zhuang, Shenghua Wang, Zi Yang, Zu‐Li Wang, Jun Jiang, Wei‐Min He
Herein, we report the sustainable semiheterogeneous synthesis of various fluoroalkylated N -heteroarenes using natural intrinsic iron(II) titanium oxide (FeTiO 3 ) as a semiconductor photocatalyst and Ph 3 N as a redox mediator. This synergistic system combines photogenerated electron-mediated fluoroalkyl sulfonyl chloride (R f SO 2 Cl) reduction with photogenerated hole-induced oxidative dehydrogenation aromatization, enabling high-yielding transformations with excellent functional-group tolerance while avoiding stoichiometric redox reagents or sacrificial electron donors/acceptors.