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dc.contributor.authorZheng, Lifeien
dc.contributor.authorSonzini, Silviaen
dc.contributor.authorAmbarwati, Masyithaen
dc.contributor.authorRosta, Edinaen
dc.contributor.authorScherman, Orenen
dc.contributor.authorHerrmann, Andreasen
dc.date.accessioned2015-08-18T15:49:30Z
dc.date.available2015-08-18T15:49:30Z
dc.date.issued2015-09-07en
dc.identifier.citationAngewandte Chemie International Edition (English) 2015, 54(44), 13007–13011. doi: 10.1002/anie.201505628en
dc.identifier.issn1433-7851
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/250307
dc.description.abstractChiral macromolecules have been widely used as synthetic pockets to mimic natural enzymes and promote asymmetric reactions. An achiral host, cucurbit[8]uril (CB[8]), 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.
dc.description.sponsorshipThis 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.
dc.languageEnglishen
dc.language.isoenen
dc.publisherWiley
dc.rightsCreative Commons Attribution 4.0
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/
dc.subjectsupramolecular chemistryen
dc.subjecthost-guest systemsen
dc.subjectmacrocyclesen
dc.subjectasymmetric catalysisen
dc.subjectDiels-Alder reactionen
dc.titleTurning cucurbit[8]uril into a supramolecular nanoreactor for asymmetric catalysisen
dc.typeArticle
dc.description.versionThis is the final version of the article. It first appeared from Wiley via http://dx.doi.org/10.1002/anie.201505628en
prism.endingPage13011
prism.publicationDate2015en
prism.publicationNameAngewandte Chemie International Edition (English)en
prism.startingPage13007
prism.volume54en
dc.rioxxterms.funderERC
dc.rioxxterms.funderEPSRC
rioxxterms.versionofrecord10.1002/anie.201505628en
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserveden
rioxxterms.licenseref.startdate2015-09-07en
dc.contributor.orcidScherman, Oren [0000-0001-8032-7166]
dc.identifier.eissn1521-3773
rioxxterms.typeJournal Article/Reviewen
pubs.funder-project-idEuropean Research Council (240629)


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Creative Commons Attribution 4.0
Except where otherwise noted, this item's licence is described as Creative Commons Attribution 4.0