Abstract: | Novel layered heterogeneous chiral salen Mn (III) catalysts anchored onto ZnPS‐PVPA by means of click chemistry are synthesized and employed in asymmetric epoxidations of unfunctionalized olefins. The catalysts manifest superior catalytic performances (conv%, up to >99; ee%, up to >99) according to the epoxidations of α‐methylstyrene, styrene, indene and 1‐octene. But for 6‐cyano‐ 2,2‐dimethylchromene and 6‐nitro‐2,2‐dimethylchromene, configuration of epoxides are reversed. Moreover, the catalysts could still indicate comparable properties (yield, 82%; ee, 86%) after recycling for nine times and excellent functions in large‐scale reactions, which paves the way for the application in industry. |