CuCo Nanoparticle, Pd(II), and l-Proline Trifunctionalized UiO-67 Catalyst for Three-Step Sequential Asymmetric Reactions.

Metal-organic frameworks (MOFs) have become a promising support for different active sites to construct multifunctional and heterogeneous catalysts. However, the related investigation mainly focuses on introducing one or two active sites into MOFs and trifunctional catalysts have been very rarely reported. Herein, non-noble CuCo alloy nanoparticles, Pd2+, and l-proline, as encapsulated active species, functional organic linkers, and active metal nodes, respectively, were successfully decorated to UiO-67 to construct a chiral trifunctional catalyst by the one-step method, which was further applied to asymmetric three-step sequential oxidation of aromatic alcohols/Suzuki coupling/asymmetric aldol reactions with excellent oxidation and coupling performance (yields up to 95 and 96%, respectively), as well as good enantioselectivities (eeanti value up to 73%) in asymmetric aldol reactions. The heterogeneous catalyst can be reused at least five times without obvious deactivation due to the strong interaction between the MOFs and the active sites. This work provides an effective strategy to construct multifunctional catalysts via the introduction and combination of three or more of active sites, including encapsulated active species, functional organic linkers, and active metal nodes, into stable MOFs.