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dc.contributor.authorGrayson, Matthewen
dc.date.accessioned2017-06-06T08:59:34Z
dc.date.available2017-06-06T08:59:34Z
dc.date.issued2017-04-21en
dc.identifier.issn0022-3263
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/264650
dc.description.abstractWe report density functional theory calculations that examine the mechanism and origins of stereoselectivity of Soós' landmark discovery from 2005 that cinchona thioureas catalyze the asymmetric Michael addition of nitroalkanes to enones. We show that the electrophile is activated by the catalyst's protonated amine and that the nucleophile binds to the thiourea moiety by hydrogen bonding. These results lead to the correction of published mechanistic work which did not consider this activation mode. We have also investigated the corresponding cinchona squaramide-catalyzed reaction and found that it proceeds by the same mechanism despite the differences in the geometry of the two catalysts' hydrogen-bond-donating groups, which demonstrates the generality of this mechanistic model.
dc.description.sponsorshipM.N.G. thanks Girton College, Cambridge (Research Fellowship) for financial support. Part of this work was performed using the Darwin Supercomputer of the University of Cambridge High Performance Computing Service (http://www.hpc.cam.ac.uk/), provided by Dell Inc. using Strategic Research Infrastructure Funding from the Higher Education Funding Council for England and funding from the Science and Technology Facilities Council.
dc.languageengen
dc.language.isoenen
dc.publisherAmerican Chemical Society
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.titleMechanism and Origins of Stereoselectivity in the Cinchona Thiourea- and Squaramide-Catalyzed Asymmetric Michael Addition of Nitroalkanes to Enonesen
dc.typeArticle
prism.endingPage4401
prism.issueIdentifier8en
prism.publicationDate2017en
prism.publicationNameThe Journal of Organic Chemistryen
prism.startingPage4396
prism.volume82en
dc.identifier.doi10.17863/CAM.10248
dcterms.dateAccepted2017-03-20en
rioxxterms.versionofrecord10.1021/acs.joc.7b00521en
rioxxterms.versionVoRen
rioxxterms.licenseref.urihttp://creativecommons.org/licenses/by/4.0/en
rioxxterms.licenseref.startdate2017-04-21en
dc.identifier.eissn1520-6904
rioxxterms.typeJournal Article/Reviewen
cam.issuedOnline2017-03-20en
cam.orpheus.successThu Jan 30 10:20:13 GMT 2020 - The item has an open VoR version.*
rioxxterms.freetoread.startdate2100-01-01


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