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Complete asymmetric induction of supramolecular chirality in a hydrogen-bonded assembly

Nature volume 398, pages 498–502 (1999)Cite this article

Abstract

Chirality at the supramolecular level involves the non-symmetric arrangement of molecular components in a non-covalent assembly1,2. Supramolecular chirality is abundant in biology, for example in the DNA double helix3, the triple helix of collagen4 and the α-helical coiled coil of myosin5. These structures are stabilized by inter-strand hydrogen bonds, and their handedness is determined by the configuration of chiral centres in the nucleotide or peptide backbone. Synthetic hydrogen-bonded assemblies have been reported that display supramolecular chirality in solution6,7,8 or in the solid state9,10,11,12. Complete asymmetric induction of supramolecular chirality—the formation of assemblies of a single handedness—has been widely studied in polymeric superstructures13,14. It has so far been achieved in inorganic metal-coordinated systems15,16,17, but not in organic hydrogen-bonded assemblies18,19,20. Here we describe the diastereoselective assembly of enantio-pure calix[4]arene dimelamines and 5,5-diethylbarbituric acid (DEB) into chiral hydrogen-bonded structures of one handedness. The system displays complete enantioselective self-resolution: the mixing of homomeric assemblies (composed of homochiral units) with opposite handedness does not lead to the formation of heteromeric assemblies. The non-covalent character of the chiral assemblies, the structural simplicity of the constituent building blocks and the ability to control the assembly process by means of peripheral chiral centres makes this system promising for the development of a wide range of homochiral supramolecular materials or enantioselective catalysts.

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Figure 1: Schematic representations and molecular structure of the nine-component hydrogen bonded assemblies 13·DEB6–53·DEB6, 63·CYA6 and 73·CYA6 with their individual components.
Figure 2: Characterization of chiral non-covalent assemblies (M)-23·DEB6 and (P)-33·DEB6 by 1H NMR spectroscopy.
Figure 3: Characterization of assemblies 23·DEB6–53·DEB6 by CD and ultraviolet spectroscopy.
Figure 4: Characterization of mixed assemblies 23−n6n·DEB6 (n = 0–3) by 1H NMR and CD spectroscopy.
Figure 5: Characterization of mixed assemblies 23−n3n·DEB6 (n = 0–3) by 1H NMR and CD spectroscopy.
Figure 6: Isomeric distribution of hydrogen-bonded assemblies from 1, (R,R)-2, and (R,S)-7 with HexCYA as determined by 1H NMR spectroscopy.

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Acknowledgements

We thank R. Hulst for the 2D ROESY experiments, R. Fokkens and N. M. M. Nibbering for the MALDI-TOF measurements, and E. W. Meijer for providing the use of the CD equipment. This work was supported by the Council for Chemical Sciences (CW) and the Technology Foundation (STW) of the Netherlands Organization for Scientific Research (NWO).

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  1. Laboratory of Supramolecular Chemistry and Technology, MESA+ Research Institute, University of Twente, PO Box 217, Enschede, 7500, AE, The Netherlands

    Leonard J. Prins, Jurriaan Huskens, Feike de Jong, Peter Timmerman & David N. Reinhoudt

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  1. Leonard J. Prins
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Correspondence to David N. Reinhoudt.

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Prins, L., Huskens, J., de Jong, F. et al. Complete asymmetric induction of supramolecular chirality in a hydrogen-bonded assembly. Nature 398, 498–502 (1999). https://doi.org/10.1038/19053

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