Turning cucurbituril into a supramolecular nanoreactor for asymmetric catalysis
Angewandte Chemie International Edition (English)
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Zheng, L., Sonzini, S., Ambarwati, M., Rosta, E., Scherman, O., & Herrmann, A. (2015). Turning cucurbituril into a supramolecular nanoreactor for asymmetric catalysis. Angewandte Chemie International Edition (English), 54 13007-13011. https://doi.org/10.1002/anie.201505628
Chiral macromolecules have been widely used as synthetic pockets to mimic natural enzymes and promote asymmetric reactions. An achiral host, cucurbituril (CB), was used for an asymmetric Lewis acid catalyzed Diels–Alder reaction. We achieved a remarkable increase in enantioselectivity and a large rate acceleration in the presence of the nanoreactor by using an amino acid as the chiral source. Mechanistic and computational studies revealed that both the amino acid–Cu2+ complex and the dienophile substrate are included inside the macrocyclic host cavity, suggesting that contiguity and conformational constraints are fundamental to the catalytic process and rate enhancement. These results pave the way towards new studies on asymmetric reactions catalyzed in confined achiral cavities.
supramolecular chemistry, host-guest systems, macrocycles, asymmetric catalysis, Diels-Alder reaction
This research was supported by the European Union (European Research Council Starting GrantsASPiRe 240629 (OAS) and NUCLEOPOLY240080 (AH) and STREP project MICREAGENTS), the Netherlands Organization for Scientific Research (NWO-Vici Grant) and the Zernike Institute for Advanced Materials. E R. acknowledges computational support from the NIH Biowulf cluster, the EPSRC UK NSCCS cluster, and the ARCHER UK National Supercomputing Service via CCPBioSim.
European Research Council (240629)
External DOI: https://doi.org/10.1002/anie.201505628
This record's URL: https://www.repository.cam.ac.uk/handle/1810/250307
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