Lead‐Free Cs 3 Bi 2 Br 9 Perovskite as Heterogeneous Photocatalyst for Oxidative Dehydrogenative Coupling of Thiols and P(O)H Compounds

An efficient and straightforward synthetic strategy has been established for the synthesis of biologically relevant thiophosphates. This method relies on visible light‐induced oxidative dehydrogenative coupling between thiols and P(O)H compounds, utilizing lead‐free Cs 3 Bi 2 Br 9 perovskite as a heterogeneous photocatalyst with air serving as the oxidant. The reaction proceeds efficiently in 2‐methyl tetrahydrofuran (2‐MeTHF) under ambient temperature conditions, exhibits good tolerance towards a wide range of functional groups, and affords the target products in high yields. Furthermore, the photocatalyst can be readily recycled for at least 5 runs in gram‐scale synthesis without a significant loss of catalytic activity.