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

With Ce@g-C₃N₄ as a heterogeneous semiconductor photocatalyst, ⁿBu₄NCl as both a redox catalyst and a hydrogen atom transfer catalyst, the first example of semiheterogeneous photocatalytic cross-dehydrogenative coupling of N-heteroarenes and alkanes/ethers with H₂ evolution was developed. Both a diverse array of high-value alkylated N-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.