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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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.
The authors declare no competing financial interests.
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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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