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Mechanism and Origins of Stereoselectivity in the Cinchona Thiourea- and Squaramide-Catalyzed Asymmetric Michael Addition of Nitroalkanes to Enones

cam.issuedOnline2017-03-20
cam.orpheus.successThu Jan 30 10:20:13 GMT 2020 - The item has an open VoR version.
dc.contributor.authorGrayson, MN
dc.date.accessioned2017-06-06T08:59:34Z
dc.date.available2017-06-06T08:59:34Z
dc.date.issued2017-04-21
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.identifier.doi10.17863/CAM.10248
dc.identifier.eissn1520-6904
dc.identifier.issn0022-3263
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/264650
dc.languageeng
dc.language.isoeng
dc.publisherAmerican Chemical Society
dc.publisher.urlhttp://dx.doi.org/10.1021/acs.joc.7b00521
dc.rightsAttribution 4.0 International
dc.rightsAttribution 4.0 International
dc.rightsAttribution 4.0 International
dc.rightsAttribution 4.0 International
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/
dc.subject0306 Physical Chemistry (incl. Structural)
dc.titleMechanism and Origins of Stereoselectivity in the Cinchona Thiourea- and Squaramide-Catalyzed Asymmetric Michael Addition of Nitroalkanes to Enones
dc.typeArticle
dcterms.dateAccepted2017-03-20
prism.endingPage4401
prism.issueIdentifier8
prism.publicationDate2017
prism.publicationNameThe Journal of Organic Chemistry
prism.startingPage4396
prism.volume82
rioxxterms.licenseref.startdate2017-04-21
rioxxterms.licenseref.urihttp://creativecommons.org/licenses/by/4.0/
rioxxterms.typeJournal Article/Review
rioxxterms.versionVoR
rioxxterms.versionofrecord10.1021/acs.joc.7b00521

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