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A series of isoreticular chiral metal–organic frameworks as a tunable platform for asymmetric catalysis

Nature Chemistry volume 2, pages 838–846 (2010)Cite this article

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Abstract

Metal–organic frameworks, built by bridging metal ions with organic linkers, represent a new class of porous hybrid materials with attractive tunability in compositions, structures and functions. In particular, the mild conditions typically employed for their synthesis allow for the functionalization of their building blocks, and thus the rational design of novel materials. Here we demonstrate the systematic design of eight mesoporous chiral metal–organic frameworks, with the framework formula [LCu2(solvent)2] (where L is a chiral tetracarboxylate ligand derived from 1,1′-bi-2-naphthol), that have the same structures but channels of different sizes. Chiral Lewis acid catalysts were generated by postsynthesis functionalization with Ti(OiPr)4, and the resulting materials proved to be highly active asymmetric catalysts for diethylzinc and alkynylzinc additions, which converted aromatic aldehydes into chiral secondary alcohols. The enantioselectivities of these reactions can be modified by tuning the size of the channels, which alters the diffusion rates of the organic substrates.

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Figure 1: Schematic representation of a homochiral MOF and its postsynthetic modification (PSM) to give a catalytically active MOF.
Figure 2: Crystal structure of CMOF-1a.
Figure 3: Space-filling models that show packing diagrams of CMOF-1b to -4b.
Figure 4: Characterization of the CMOF series.
Figure 5: CMOF-derived asymmetric catalysts and their framework stability.
Figure 6: Asymmetric diethylzinc and alkynylzinc additions catalysed by the CMOF/Ti(OiPr)4 catalyst.

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Acknowledgements

We thank the National Science Foundation (CHE-0512495 and -0809776) for generous support of this research and R. Huxford for experimental help.

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  1. Liqing Ma and Joseph M. Falkowski: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Chemistry, CB#3290, University of North Carolina, Chapel Hill, North Carolina, 27599, USA

    Liqing Ma, Joseph M. Falkowski, Carter Abney & Wenbin Lin

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  1. Liqing Ma
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Contributions

L.M., J.M.F., C.A. and W.L. designed and conducted the research. L.M., J.M.F. and W.L. co-wrote the paper.

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Correspondence to Wenbin Lin.

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Supplementary information

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Supplementary information (PDF 2307 kb)

Supplementary information

Crystallographic data for compound CMOF-1a (CIF 13 kb)

Supplementary information

Crystallographic data for compound CMOF-2a (CIF 13 kb)

Supplementary information

Crystallographic data for compound CMOF-2b (CIF 12 kb)

Supplementary information

Crystallographic data for compound CMOF-3b (CIF 14 kb)

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Crystallographic data for compound CMOF-4a (CIF 15 kb)

Supplementary information

Crystallographic data for compound CMOF-4b (CIF 15 kb)

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Ma, L., Falkowski, J., Abney, C. et al. A series of isoreticular chiral metal–organic frameworks as a tunable platform for asymmetric catalysis. Nature Chem 2, 838–846 (2010). https://doi.org/10.1038/nchem.738

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