A multifunctional magnetic chiral metal-organic framework (MOF) was developed for asymmetric applications by utilizing strategies of chiralization and multifunctionalization. Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 was employed as a chiral secondary agent to synthesize a chiral hybrid nanocomposite within a MOF. The use of a chiral secondary agent efficiently induces chirality in an achiral MOF structure that cannot be directly chiralized. The HKUST-1@Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 nanocomposite was afforded by first anchoring chiral Cu(l-proline)2 on the Triazine/Fe3O4@SiO2-NH2 surface and then encapsulating the Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 nanoparticles with HKUST-1 via in situ ultrasonication synthesis. In the synthesis of the HKUST-1@Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 nanocomposite, Cu(l-proline)2 was used as a chiral complex due to its Lewis acidic/basic hydroxyl groups, carboxylate carbonyl functional groups acting as Lewis bases, an active Cu site functioning as a Lewis acid center, and azine groups of TCT acting as Lewis bases, all synergistically interacting with the Lewis acidity of the Cu centers in HKUST-1. To assess these synergic effects, HKUST-1@Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 was used in the formation of an asymmetric C-C bond in nitroaldol condensation and asymmetric cycloaddition of CO2 to epoxides. The findings demonstrated that under mild and green conditions, in both the asymmetric nitroalcohol condensation and the asymmetric cycloaddition of CO2, HKUST-1@Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 had better enantioselectivity than the Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 nanoparticles and a higher selectivity toward β-nitroalcohol and cyclic carbonate over the pure HKUST-1. Despite its simple and easy synthesis, HKUST-1@Cu(l-proline)2-Triazine/Fe3O4@SiO2-NH2 exhibited exceptional performance in the asymmetric nitroaldol condensation and asymmetric cycloaddition of CO2 to epoxides. Additionally, the mechanism of the reactions was depicted with reference to the total energy of the reactants, intermediates, and products.
Keywords: CO2 fixation; Henry reaction; heterogeneous catalysis; magnetic chiral nanocomposite.