One‐Pot Multifunctional Catalysis with NNN‐Pincer Zr‐MOF: Zr Base Catalyzed Condensation with Rh‐Catalyzed Hydrogenation

Abstract

Abstract We describe the postsynthetic modification of Zr‐based metal organic frameworks (MOFs) containing chiral NNN‐pincer ligands based on aminopyridineimines, as well as the subsequent formation of (NNN)‐M‐Zr‐MOF complexes (M=Rh, Ir). With these new multifunctional materials, we performed a cascade of condensation reactions followed by hydrogenation of the resulting double bond. If the condensation reaction occurs between an aldehyde and ethyl nitroacetate, (NNN)–M–Zr‐MOF complexes catalyze the one‐pot synthesis of nitroalkenes, in which Zr IV Lewis sites play a role similar to that of the generally used Ti IV in homogeneous catalysis. These multifunctional hybrid catalysts retain their crystalline framework even after the reaction, and they were isolated easily from the reaction mixture through filtration and reused several times without a significant degradation in activity. Moreover, there was no contribution from leached active species and conversion was possible only in the presence of the solid catalyst.