Design and Assembly of Chiral Coordination Cages for Asymmetric Sequential Reactions

• Published in: Journal of the American Chemical Society Vol. 140; no. 6; pp. 2251 - 2259
• Main Authors: Jiao, Jingjing, Tan, Chunxia, Li, Zijian, Liu, Yan, Han, Xing, Cui, Yong
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 14.02.2018; Amer Chemical Soc
• Subjects: active sites; catalysts; catalytic activity; Chemistry; Chemistry, Multidisciplinary; chromium; dicarboxylic acids; enantiomers; enantioselectivity; energy-dispersive X-ray analysis; epoxidation reactions; hydrophobicity; iron; ligands; manganese; Physical Sciences; Science & Technology; spectrometers; EPOXIDES; EFFICIENT CATALYSIS; SALEN COMPLEXES; STRATEGY; METAL-ORGANIC FRAMEWORK; HOST; SUPRAMOLECULAR CATALYSIS; SEPARATION; TETRAHEDRAL CAGES; EPOXIDATION
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.7b11679

Supramolecular nanoreactors featuring multiple catalytically active sites are of great importance, especially for asymmetric catalysis, and are yet challenging to construct. Here we report the design and assembly of five chiral single- and mixed-linker tetrahedral coordination cages using six dicarboxylate ligands derived-from enantiopure Mn­(salen), Cr­(salen) and/or Fe­(salen) as linear linkers and four Cp3Zr3 clusters as three-connected vertices. The formation of these cages was confirmed by a variety of techniques including single-crystal and powder X-ray diffraction, inductively coupled plasma optical emission spectrometer, quadrupole-time-of-flight mass spectrometry and energy dispersive X-ray spectrometry. The cages feature a nanoscale hydrophobic cavity decorated with the same or different catalytically active sites, and the mixed-linker cage bearing Mn­(salen) and Cr­(salen) species is shown to be an efficient supramolecular catalyst for sequential asymmetric alkene epoxidation/epoxide ring-opening reactions with up to 99.9% ee. The cage catalyst demonstrates improved activity and enantioselectivity over the free catalysts owing to stabilization of catalytically active metallosalen units and concentration of reactants within the cavity. Manipulation of catalytic organic linkers in cages can control the activities and selectivities, which may provide new opportunities for the design and assembly of novel functional supramolecular architectures.