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dc.contributor.authorStark, Daniel Graham
dc.contributor.authorWilliamson, Patrick
dc.contributor.authorGayner, Emma R
dc.contributor.authorMusolino, Stefania Francesca
dc.contributor.authorKerr, Ryan William Frederick
dc.contributor.authorTaylor, James Edward
dc.contributor.authorSlawin, Alexandra Martha Zoya
dc.contributor.authorO'Riordan, Timothy J C
dc.contributor.authorMacgregor, Stuart A
dc.contributor.authorSmith, Andrew David
dc.date.accessioned2016-08-19T10:30:14Z
dc.date.available2016-08-19T10:30:14Z
dc.date.issued2016-10-14
dc.identifier.citationStark , D G , Williamson , P , Gayner , E R , Musolino , S F , Kerr , R W F , Taylor , J E , Slawin , A M Z , O'Riordan , T J C , Macgregor , S A & Smith , A D 2016 , ' Isothiourea-catalysed enantioselective pyrrolizine synthesis : synthetic and computational studies ' , Organic & Biomolecular Chemistry , vol. 14 , no. 38 , pp. 8957-8965 . https://doi.org/10.1039/C6OB01557Cen
dc.identifier.issn1477-0520
dc.identifier.otherPURE: 244482624
dc.identifier.otherPURE UUID: df25d7fa-3866-4593-a3f8-5538ca04a20e
dc.identifier.otherScopus: 84989257470
dc.identifier.otherORCID: /0000-0002-2104-7313/work/36567486
dc.identifier.otherORCID: /0000-0002-9527-6418/work/56861937
dc.identifier.otherWOS: 000385173200010
dc.identifier.urihttp://hdl.handle.net/10023/9335
dc.descriptionWe thank Syngenta and the EPSRC (grant code EP/K503162/1) (DGS), and the EPSRC Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT, grant code EP/L016419/1) (ERG,SFM, RWFK) for funding. The European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013) ERC Grant Agreement No. 279850 is also acknowledged (JET). ADS thanks the Royal Society for a Wolfson Research Merit Award.en
dc.description.abstractThe catalytic enantioselective synthesis of a range of cis-pyrrolizine carboxylate derivatives with outstanding stereocontrol (14 examples,>95:5 dr, >98:2 er) through an isothiourea-catalyzed intramolecular Michael addition-lactonisation and ring opening approach from the corresponding enone acid is reported. An optimised and straightforward three-step synthetic route to the enone acid starting materials from readily available pyrrole-2-carboxaldehydes is delineated, with benzotetramisole (5 mol%) proving the optimal catalyst for the enantioselective process. Ring-opening of the pyrrolizine dihydropyranone products with either MeOH or a range of amines leads to the desired products in excellent yield and enantioselectivity. Computation has been used to probe the factors leading to high stereocontrol, with the formation of the observed cis-steroisomer predicted to be kinetically and thermodynamically favoured.
dc.format.extent9
dc.language.isoeng
dc.relation.ispartofOrganic & Biomolecular Chemistryen
dc.rightsCopyright 2016 the Authors. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.en
dc.subjectQD Chemistryen
dc.subjectDASen
dc.subject.lccQDen
dc.titleIsothiourea-catalysed enantioselective pyrrolizine synthesis : synthetic and computational studiesen
dc.typeJournal articleen
dc.contributor.sponsorEPSRCen
dc.contributor.sponsorThe Royal Societyen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.contributor.institutionUniversity of St Andrews. Biomedical Sciences Research Complexen
dc.contributor.institutionUniversity of St Andrews. EaSTCHEMen
dc.identifier.doihttps://doi.org/10.1039/C6OB01557C
dc.description.statusPeer revieweden
dc.identifier.urlhttp://www.rsc.org/suppdata/c6/ob/c6ob01557c/c6ob01557c1.zipen
dc.identifier.urlhttp://www.rsc.org/suppdata/c6/ob/c6ob01557c/c6ob01557c2.pdfen
dc.identifier.grantnumberEP/L016419/1en
dc.identifier.grantnumberWM140071en


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