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. 2017 Dec 19;8(1):2171.
doi: 10.1038/s41467-017-02335-0.

Sixteen isostructural phosphonate metal-organic frameworks with controlled Lewis acidity and chemical stability for asymmetric catalysis

Xu Chen  1 , Yongwu Peng  1 , Xing Han  1 , Yan Liu  2 , Xiaochao Lin  1 , Yong Cui  3   4
Affiliations

Sixteen isostructural phosphonate metal-organic frameworks with controlled Lewis acidity and chemical stability for asymmetric catalysis

Xu Chen et al. Nat Commun. .

Abstract

Heterogeneous catalysts typically lack the specific steric control and rational electronic tuning required for precise asymmetric catalysis. Here we demonstrate that a phosphonate metal-organic framework (MOF) platform that is robust enough to accommodate up to 16 different metal clusters, allowing for systematic tuning of Lewis acidity, catalytic activity and enantioselectivity. A total of 16 chiral porous MOFs, with the framework formula [M3 L 2(solvent)2] that have the same channel structures but different surface-isolated Lewis acid metal sites, are prepared from a single phosphono-carboxylate ligand of 1,1'-biphenol and 16 different metal ions. The phosphonate MOFs possessing tert-butyl-coated channels exhibited high thermal stability and good tolerances to boiling water, weak acid and base. The MOFs provide a versatile family of heterogeneous catalysts for asymmetric allylboration, propargylation, Friedel-Crafts alkylation and sulfoxidation with good to high enantioselectivity. In contrast, the homogeneous catalyst systems cannot catalyze the test reactions enantioselectively.

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Conflict of interest statement

The authors declare no competing financial interests.

Figures

Fig. 1
Fig. 1
Synthesis and X-ray crystal structure of 1-M. a Synthesis of the isostructural series of 1-M from H3 L and different metal ions (only the coordinated oxygen atoms were shown for OAc− anions in 1-M(III) and 1-M(IV). Green, M; gold, P; red, O; blue, C). b The 3D hydrophobic structure of 1-M along the c-axis (the metal ions are shown in polyhedral). c A portion of the 3D structure highlighting the exposure of the SBUs to the pores
Fig. 2
Fig. 2
PXRD patterns of 1-M. a, b The as-prepared 1-M. c 1-Cr and 1-Mn after 7 days treatment under different conditions. d 1-Zr and 1-Mg after 7 days treatment under different conditions
Fig. 3
Fig. 3
N2 sorption isotherms. N2 adsorption isotherms (filled symbols) and desorption isotherms (open symbols) at 77 K of MOFs 1-Cr (a), 1-Mg (b), 1-Mn (c), and 1-Zr (d) after treatment under different conditions
Fig. 4
Fig. 4
Schematic representation of production elaboration. a The synthesis of 3,4-allenol and b pyrrolo[3,2-c]pyridine
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