Substrate Selectivity Imparted by Self‐Assembled Molecular Containers and Catalysts

Recent trends in catalysis are devoted to mimicking some peculiar features of enzymes like site selectivity, through functional group recognition, and substrate selectivity, through recognition of the entire surface of the substrate. The latter is a specific feature of enzymes that is seldomly present in homogeneous catalysis. Supramolecular catalysis, thanks to the self‐assembly of simple subunits, enables the creation of cavities and surfaces whose confinement effects drive the preferential binding of a substrate among others with consequent substrate selectivity. The topic is an emerging field that exploits recognition phenomena to discriminate the reagents based on their size and shape. This review deals this cutting‐edge field of research covering examples of supramolecular self‐assembled molecular containers and catalysts operating in organic as well as aqueous media, with special emphasis for catalytic systems dealing with direct competitive experiments involving two or more substrates. Substrate selectivity is the property of catalysts like enzymes to pick up one substrate among many others in solution. To implement substrate selectivity in artificial homogeneous catalysts, an emerging approach in homogeneous catalysis consists in exploiting self‐assembled nano‐catalysts and nanocontainers. The confinement effects provide supramolecular substrate recognition before the catalytic step. This review covers recent achievements in this challenging field of research.