Dual Ce@g-C₃N₄-Photoredox/Chlorine Catalysis: Cross-Dehydrogenative Coupling of <i>N</i>-Heteroarenes and Alkanes/Ethers with H₂ Evolution

With Ce@g-C₃N₄ as a heterogeneous semiconductor photocatalyst, ^<i>n</i>Bu₄NCl as both a redox catalyst and a hydrogen atom transfer catalyst, the first example of semiheterogeneous photocatalytic cross-dehydrogenative coupling of <i>N</i>-heteroarenes and alkanes/ethers with H₂ evolution was developed. Both a diverse array of high-value alkylated <i>N</i>-heteroarenes and clean H₂ can be efficiently coproduced under sacrificial reagent- and chemical oxidant/reductant-free conditions. Combining both the reversible Ce⁴⁺/Ce³⁺ redox pair and the reversible Cl̅/Cl ̇ redox pair can considerably improve the photocatalytic efficiency.