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dc.contributor.authorMcLaughlin, Calum
dc.contributor.authorSlawin, Alexandra M. Z.
dc.contributor.authorSmith, Andrew D.
dc.date.accessioned2020-09-11T23:36:56Z
dc.date.available2020-09-11T23:36:56Z
dc.date.issued2019-10-14
dc.identifier.citationMcLaughlin , C , Slawin , A M Z & Smith , A D 2019 , ' Base-free enantioselective C(1)-ammonium enolate catalysis exploiting aryloxides : a synthetic and mechanistic study ' , Angewandte Chemie International Edition , vol. 58 , no. 42 , pp. 15111-15119 . https://doi.org/10.1002/anie.201908627en
dc.identifier.issn1433-7851
dc.identifier.otherPURE: 260858128
dc.identifier.otherPURE UUID: b0468a74-8857-48c4-86e6-d971fecbb50f
dc.identifier.otherORCID: /0000-0002-2104-7313/work/61621994
dc.identifier.otherORCID: /0000-0002-9527-6418/work/61622013
dc.identifier.otherScopus: 85072992478
dc.identifier.otherWOS: 000485505100001
dc.identifier.urihttp://hdl.handle.net/10023/20611
dc.descriptionWe thank the European Research Council under the European Union's Seventh Framework Programme (FP7/2007-2013) ERC grant agreement no. 279850 (A.D.S) and the EPSRC (EP/M508214/1, C.M.) for funding. A.D.S. thanks the Royal Society for a Wolfson Research Merit Award.en
dc.description.abstractAn isothiourea‐catalyzed enantioselective Michael addition of aryl ester pronucleophiles to vinyl bis‐sulfones via C(1)‐ammonium enolate intermediates has been developed. This operationally simple method allows the base‐free functionalization of aryl esters to form α‐functionalized products containing two contiguous tertiary stereogenic centres in excellent yield and stereoselectivity (all ≥ 99:1 er). Key to the success of this methodology is the multifunctional role of the aryloxide, which operates as a leaving group, Brønsted base, Brønsted acid and Lewis base within the catalytic cycle. Comprehensive mechanistic studies, including variable time normalization analysis (VTNA) and isotopologue competition experiments, have been carried out. These studies have identified (i) orders of all reactants; (ii) a turnover‐limiting Michael addition step, (iii) product inhibition, (iv) the catalyst resting state and (v) catalyst deactivation through protonation.
dc.format.extent9
dc.language.isoeng
dc.relation.ispartofAngewandte Chemie International Editionen
dc.rightsCopyright © 2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1002/anie.201908627en
dc.subjectEnantioselective Michael additionen
dc.subjectInverse secondary kinetic isotope effecten
dc.subjectIsothiourea catalysisen
dc.subjectMechanistic analysisen
dc.subjectVTNAen
dc.subjectQD Chemistryen
dc.subjectDASen
dc.subjectBDCen
dc.subjectR2Cen
dc.subject.lccQDen
dc.titleBase-free enantioselective C(1)-ammonium enolate catalysis exploiting aryloxides : a synthetic and mechanistic studyen
dc.typeJournal articleen
dc.description.versionPostprinten
dc.contributor.institutionUniversity of St Andrews.University of St Andrewsen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.Biomedical Sciences Research Complexen
dc.identifier.doihttps://doi.org/10.1002/anie.201908627
dc.description.statusPeer revieweden
dc.date.embargoedUntil2020-09-12


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