Step-by-Step Assembly of 2D Confined Chiral Space Endowing Achiral Clusters with Asymmetric Catalytic Activity for Epoxidation of Allylic Alcohols.

Endowing achiral polyoxometalates (POMs) with asymmetric catalytic properties is always an intriguing but challenging topic because of their high catalytic activities yet highly symmetrical molecular structures. In this work, a novel strategy was proposed to fabricate a series of two-dimensional chiral POM catalysts. Following the steps of exfoliation, covalent modification, and reassembly, the achiral POMs were orderly confined into the chiral interstitial domains of chiral ionic liquid (CIL)-modified layered double hydroxide materials with a decreased molecular symmetry. The chirality of POM molecules was induced by the l- or d-pyrrolidine-type CILs, and their asymmetric catalytic activity was enhanced by the confinement effect. Compared with the reported chiral POM-based catalysts [e.g., 8 turnover frequency (TOF) and 79% enantiomeric excess (ee) for chiral POM-based metal-organic frameworks], the constructed chiral POM catalysts showed a significantly higher TOF and enantioselectivity (up to 240 TOF and 93% ee) for the asymmetric epoxidation of allylic alcohols. The facilitated mass transfer in the IL channels and the increased binding efficiency between the chiral catalytic sites and reactants render this strategy highly promising for constructing efficient chiral catalysts from the catalytically active while achiral building blocks.