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dc.contributor.authorWang, Yihong
dc.contributor.authorYoung, Claire Mary
dc.contributor.authorLiu, Honglei
dc.contributor.authorHartley, Will
dc.contributor.authorWienhold, Max
dc.contributor.authorCordes, David Bradford
dc.contributor.authorSlawin, Alexandra Martha Zoya
dc.contributor.authorSmith, Andrew David
dc.identifier.citationWang , Y , Young , C M , Liu , H , Hartley , W , Wienhold , M , Cordes , D B , Slawin , A M Z & Smith , A D 2022 , ' A desilylative approach to alkyl substituted C(1)-ammonium enolates : application in enantioselective [2+2] cycloadditions ' , Angewandte Chemie International Edition , vol. 61 , no. 38 , e202208800 .
dc.identifier.otherPURE: 280489269
dc.identifier.otherPURE UUID: 0c4e5f47-97da-4784-9e55-88bffab77e90
dc.identifier.otherORCID: /0000-0002-9527-6418/work/117211202
dc.identifier.otherORCID: /0000-0002-5366-9168/work/117211250
dc.identifier.otherORCID: /0000-0002-2104-7313/work/117211347
dc.identifier.otherScopus: 85135705428
dc.identifier.otherWOS: 000837483400001
dc.descriptionFunding: The research leading to these results has received funding from the CSC-St Andrews PhD Scholarship Scheme (Y.W.), the Newton Fellowship Programme (H.L.) and the Engineering and Physical Sciences Research Council, University of St Andrews, and the EPSRC Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT) for financial support [Ph.D. studentship to W. H.; Grant code: EP/L016419/1].en
dc.description.abstractThe catalytic generation of C(1)-ammonium enolates from the corresponding α-silyl-α-alkyl substituted carboxylic acids using the isothiourea HyperBTM is reported. This desilylative approach grants access to α-unsubstituted and α-alkyl substituted C(1)-ammonium enolates, which are typically difficult to access through traditional methods reliant upon deprotonation. The scope and limitations of this process is established in enantioselective [2+2]-cycloaddition processes with perfluoroalkylketones (31 examples, up to 96% yield and >99:1 er), as well as selective [2+2]-cycloaddition with trifluoromethyl enones (4 examples, up to 75% yield and >99:1 er). Preliminary mechanistic studies indicate this process proceeds through an initial kinetic resolution of an in situ prepared (±)-α-silyl-α-alkyl substituted anhydride, while the reaction process exhibits overall pseudo zero-order kinetics.
dc.relation.ispartofAngewandte Chemie International Editionen
dc.rightsCopyright © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.en
dc.subjectQD Chemistryen
dc.titleA desilylative approach to alkyl substituted C(1)-ammonium enolates : application in enantioselective [2+2] cycloadditionsen
dc.typeJournal articleen
dc.contributor.sponsorThe Royal Societyen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.contributor.institutionUniversity of St Andrews. Institute of Behavioural and Neural Sciencesen
dc.contributor.institutionUniversity of St Andrews. EaSTCHEMen
dc.description.statusPeer revieweden

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