Antonio Rescifina

In recent decades, many efforts have been devoted to studying reactions catalyzed in nanoconfined spaces. The most impressive aspect of catalysis in nanoconfined spaces is that the reactivity of the molecules can be smartly driven to disobey classical behavior. A green and efficient three‐component aza‐Darzens (TCAD) reaction using a catalytic amount of γ‐cyclodextrins (CDs) in water has been developed to synthesize N ‐phenylaziridines. CDs effectively performed this reaction in an environmentally friendly setting, achieving good yields. The same reaction was then performed using polymeric γ‐CD such as a γ‐cyclodextrin polymer crosslinked (GCDPC) with epichlorohydrin, a sponge‐like macroporous γ‐cyclodextrin‐based cryogel (GCDC), and a γ‐cyclodextrin‐based hydrogel (GCDH). The homogeneous and heterogeneous catalyst recovery was then studied, and it was proved to be easily recycled several times without relevant activity loss. Water, as a unique and eco‐friendly reaction medium, has been utilized for the first time, to the best of our knowledge, in this reaction. The inclusion of the reagents in CDs has been studied and rationalized by NMR spectroscopy experiments and molecular modeling calculations. The credit of the presented protocol includes good yields and catalyst reusability and precludes the use of organic solvents.