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dc.contributor.authorYoung, Claire Mary
dc.contributor.authorElmi, Alex
dc.contributor.authorPascoe, Dominic J.
dc.contributor.authorMorris, Rylie K.
dc.contributor.authorMcLaughlin, Calum
dc.contributor.authorWoods, Andrew
dc.contributor.authorFrost, Aileen
dc.contributor.authorDe La Houpliere, Alix
dc.contributor.authorLing, Kenneth B.
dc.contributor.authorSmith, Terry K
dc.contributor.authorSlawin, Alexandra Martha Zoya
dc.contributor.authorWilloughby, Patrick H.
dc.contributor.authorCockroft, Scott L.
dc.contributor.authorSmith, Andrew David
dc.date.accessioned2021-02-03T00:36:52Z
dc.date.available2021-02-03T00:36:52Z
dc.date.issued2020-02-17
dc.identifier264359010
dc.identifierc415814a-f29e-4891-ae49-ee57521f3775
dc.identifier85078967216
dc.identifier000510497500001
dc.identifier.citationYoung , C M , Elmi , A , Pascoe , D J , Morris , R K , McLaughlin , C , Woods , A , Frost , A , De La Houpliere , A , Ling , K B , Smith , T K , Slawin , A M Z , Willoughby , P H , Cockroft , S L & Smith , A D 2020 , ' The importance of 1,5-oxygen···chalcogen interactions in enantioselective isochalcogenourea catalysis ' , Angewandte Chemie International Edition , vol. 59 , no. 9 , pp. 3705-3710 . https://doi.org/10.1002/anie.201914421en
dc.identifier.issn1433-7851
dc.identifier.otherORCID: /0000-0002-2104-7313/work/68647561
dc.identifier.otherORCID: /0000-0002-9527-6418/work/68647737
dc.identifier.urihttps://hdl.handle.net/10023/21358
dc.descriptionSyngenta (Case Award to DJP) and a Philip Leverhulme Prize for funding (SLC, AE). RKM and PHW are grateful to the American Chemical Society Petroleum Research Fund and National Science Foundation (NSF-MRI: CHE-1429616).en
dc.description.abstractThe importance of 1,5-O···chalcogen (Ch) interactions in isochalcogenourea catalysis (Ch = O, S, Se) is investigated. Conformational analyses of N-acyl isochalcogenouronium species and comparison with kinetic data demonstrate the significance of 1,5-O···Ch interactions in enantioselective catalysis. Importantly, the selenium analogue demonstrates enhanced rate and selectivity profiles across a range of reaction processes including nitronate conjugate addition and formal [4+2] cycloadditions. A gram-scale synthesis of the most active selenium analogue was developed using a previously unreported seleno-Hugerschoff reaction, allowing the challenging kinetic resolutions of tertiary alcohols to be performed at 500 ppm catalyst loading. Density Functional Theory (DFT) and natural bond orbital (NBO) calculations support the role of orbital delocalization (occurring by intramolecular chalcogen bonding) in determining the conformation, equilibrium population, and reactivity of N-acylated intermediates.
dc.format.extent1316688
dc.language.isoeng
dc.relation.ispartofAngewandte Chemie International Editionen
dc.subjectOrganocatalysisen
dc.subjectChalcogen bondingen
dc.subjectIsothioureasen
dc.subjectIsoselenoureasen
dc.subject1,5-O···Chen
dc.subjectAsymmetric catalysisen
dc.subjectQD Chemistryen
dc.subjectDASen
dc.subjectBDCen
dc.subjectR2Cen
dc.subject.lccQDen
dc.titleThe importance of 1,5-oxygen···chalcogen interactions in enantioselective isochalcogenourea catalysisen
dc.typeJournal articleen
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.contributor.institutionUniversity of St Andrews. University of St Andrewsen
dc.contributor.institutionUniversity of St Andrews. EaSTCHEMen
dc.contributor.institutionUniversity of St Andrews. Biomedical Sciences Research Complexen
dc.contributor.institutionUniversity of St Andrews. School of Biologyen
dc.identifier.doi10.1002/anie.201914421
dc.description.statusPeer revieweden
dc.date.embargoedUntil2021-02-03


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