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Self-assembled nanospheres with multiple endohedral binding sites pre-organize catalysts and substrates for highly efficient reactions

Nature Chemistry volume 8, pages 225–230 (2016)Cite this article

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Abstract

Tuning reagent and catalyst concentrations is crucial in the development of efficient catalytic transformations. In enzyme-catalysed reactions the substrate is bound—often by multiple non-covalent interactions—in a well-defined pocket close to the active site of the enzyme; this pre-organization facilitates highly efficient transformations. Here we report an artificial system that co-encapsulates multiple catalysts and substrates within the confined space defined by an M12L24 nanosphere that contains 24 endohedral guanidinium-binding sites. Cooperative binding means that sulfonate guests are bound much more strongly than carboxylates. This difference has been used to fix gold-based catalysts firmly, with the remaining binding sites left to pre-organize substrates. This strategy was applied to a Au(I)-catalysed cyclization of acetylenic acid to enol lactone in which the pre-organization resulted in much higher reaction rates. We also found that the encapsulated sulfonate-containing Au(I) catalysts did not convert neutral (acid) substrates, and so could have potential in the development of substrate-selective catalysis and base-triggered on/off switching of catalysis.

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Figure 1: Synthesis and characterization of the M12L24 spheres that bear endohedral guanidinium-binding sites.
Figure 2: The reaction progress for the conversion of 4 is displayed for different catalysts.
Figure 3: Schematic representation of the base-triggered catalytic gating process.

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Acknowledgements

Financial support was provided by the University of Amsterdam and by the European Research Council (Advanced Grant C.2322.0269). P. Li and W. I. Dzik are acknowledged for X-ray crystallography studies. B. de Bruin, J. I. van der Vlugt, W. I. Dzik and R. Gramage-Doria are also acknowledged for helpful discussions.

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Author notes

  1. Qi-Qiang Wang

    Present address: Present address: CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences (ICCAS), Beijing 100190, China,

Authors and Affiliations

  1. Homogeneous, Supramolecular and Bio-Inspired Catalysis, Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, Amsterdam, 1098XH, The Netherlands

    Qi-Qiang Wang, Sergio Gonell, Stefan H. A. M. Leenders & Joost N. H. Reek

  2. Department Chemie und Pharmazie, Lehrstuhl für Bioanorganische Chemie, Friedrich-Alexander-Universitaet Erlangen, Egerlandstrasse 3, Erlangen, 91058, Germany

    Maximilian Dürr & Ivana Ivanović-Burmazović

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Contributions

J.N.H.R. and Q.Q.W. conceived and designed the experiments. Q.Q.W. and S.G. performed the experiments and analysed the data. M.D. and I.I.-B. carried out the CSI-MS measurements and analysed the data. J.N.H.R. and Q.Q.W. wrote the manuscript. J.N.H.R., Q.Q.W., S.G. and S.H.A.M.L. discussed the results and edited the manuscript.

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Correspondence to Joost N. H. Reek.

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The authors declare no competing financial interests.

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Crystallographic data for compound 1. (CIF 694 kb)

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Wang, QQ., Gonell, S., Leenders, S. et al. Self-assembled nanospheres with multiple endohedral binding sites pre-organize catalysts and substrates for highly efficient reactions. Nature Chem 8, 225–230 (2016). https://doi.org/10.1038/nchem.2425

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