Polyoxometalate‐based Inorganic‐Organic Hybrids as Heterogeneous Catalysts for Asymmetric and Tandem Reactions

Abstract Chiral and bi/multifunctional catalysts have contributed to the sustainability of organic transformations. Polyoxometalates (POMs) with diverse structures, good redox properties and oxidation abilities offer excellent opportunities in the area of asymmetric and one‐pot tandem reactions. However, the potential applications of POM catalysts are limited due to their solubility in many solvents. One approach to cope with this problem is to combine them with organic units and generate POM‐based inorganic‐organic hybrid materials with unique structural characteristics. This review presents the targeted design of POM‐based hybrids as heterogeneous catalysts for asymmetric and one‐pot tandem reactions. Chirality induction from chiral POMs and/or organic linkers to the whole hybrid material as well as the possibility of self‐assembly of building units via non‐covalent interactions are described. It also discusses the catalytic sites ranging from POM salts to 3D POM‐based frameworks with the focus on organic transformations such as oxidation, esterification and C−C bond formation.