Pd(II)-Metalated and l-Proline-Decorated Multivariate UiO-67 as Bifunctional Catalyst for Asymmetric Sequential Reactions

• Published in: Catalysis letters Vol. 152; no. 4; pp. 1160 - 1169
• Main Authors: Cheng, Lin, Cao, Liumei, Ren, Hao, Guo, Qiaoqiao, Deng, Huifang, Li, Yiming
• Format: Journal Article
• Language: English
• Published: New York Springer US 01.04.2022; Springer Nature; Springer; Springer Nature B.V
• Subjects: Acids; Adsorption; Aldehydes; Asymmetry; Cascade chemical reactions; Catalysis; Catalysts; Catalytic activity; Chemistry; Chemistry and Materials Science; Chemistry, Physical; Construction; Coupling (molecular); Decoration; Emission analysis; Inductively coupled plasma; Industrial Chemistry/Chemical Engineering; Leaching; Ligands; Metal-organic frameworks; Multivariate analysis; Organometallic Chemistry; Palladium; Palladium catalysts; Physical Chemistry; Physical Sciences; Proline; Science & Technology; Structural stability; Heterogeneous catalyst; Asymmetric sequential reactions; Bifunctional catalyst; UiO-67; Chiral proline; TRANSFORMATION; TANDEM CATALYSIS; SITE; POSTSYNTHETIC MODIFICATION; METAL-ORGANIC FRAMEWORKS; ZIRCONIUM; ROBUST; FUNCTIONAL-GROUPS; LIGAND; HETEROGENEOUS CATALYSTS
• ISSN: 1011-372X; 1572-879X
• DOI: 10.1007/s10562-021-03719-0

The construction of a multifunctional catalyst for multistep sequential\tandem reactions at the molecular level faces a formidable challenge. Multivariate (MTV)-MOFs can provide a facile and tunable platform for rationally designing such multifunctional catalysts via grafting different catalytic groups on the bridging ligands. However, the related investigations are still limited. Here, Pd(II) and l -proline are metalated and decorated to organic linkers, respectively, to build a MTV-MOF, which is then successfully applied to sequential Suzuki Coupling/asymmetric Aldol reactions with satisfied coupling performance (yields up to 99%) and good enantioselectivities ( ee anti up to 98%). Inductively coupled plasma optical emission spectrometer (ICP-OES) measurements of the supernatant and hot leaching test suggest the heterogeneous nature of the catalyst. Macrosubstrate tests verify that the reaction occurs inside the pores of the MOF. The heterogeneous catalyst can maintain structural stability and catalytic activity within three cycles. Graphic Abstract Versatile Pd(II) and l -proline were metalated and decorated, respectively, into stable UiO-67 to construct bifunctional and heterogeneous multivariate MOF catalyst, which displayed efficient and recyclable catalytic activity in sequential Suzuki Coupling/asymmetric Aldol reactions.