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dc.contributor.authorTenza, Kenny
dc.contributor.authorNorthen, Julian S.
dc.contributor.authorO'Hagan, David
dc.contributor.authorSlawin, Alexandra Martha Zoya
dc.identifier.citationTenza , K , Northen , J S , O'Hagan , D & Slawin , A M Z 2005 , ' Stereoselective alpha-fluoroamide and alpha-fluoro-gamma-lactone synthesis by an asymmetric zwitterionic aza-Claisen rearrangement ' , Beilstein Journal of Organic Chemistry , vol. 1 , no. 13 , 13 .
dc.identifier.otherPURE: 670997
dc.identifier.otherPURE UUID: 3a7a3cdc-9070-455b-8171-e8cfca1e676c
dc.identifier.otherWOS: 000241017700001
dc.identifier.otherScopus: 33845694441
dc.identifier.otherORCID: /0000-0002-9527-6418/work/56861723
dc.identifier.otherORCID: /0000-0002-0510-5552/work/68281255
dc.description.abstractBackground: Asymmetric introduction of fluorine alpha- to a carbonyl has become popular recently, largely because the direct fluorination of enolates by asymmetric electrophilic fluorinating reagents has improved, and as a result such compounds are becoming attractive synthons. We have sought an alternative but straightforward asymmetric method to this class of compounds, utilising the zwitterionic aza-Claisen rearrangement by reacting alpha-fluoroacid chlorides and homochiral N-allylpyrrolidines as starting materials. Results: Treatment of N-allylmorpholine with 2-fluoropropionyl chloride under Yb(OTf)(3) catalysis generated the zwitterionic aza-Claisen rearrangement product in good yield and demonstrated the chemical feasibility of the approach. For the asymmetric reaction, N-allyl-(S)-2( methoxymethyl) pyrrolidine was treated with either 2-fluoropropionyl chloride or 2-fluorophenylacetic acid chloride under similar conditions and resulted in N-(alpha-fluoro-gamma-vinylamide) pyrrolidine products as homochiral materials in 99% de. These products were readily converted to their corresponding alpha-fluoro-gamma-lactones by iodolactonisation and in good diastereoselectivity. Conclusion: Molecules which have fluorine at a stereogeneic centre are finding increasing utility in pharmaceutical, fine chemicals and materials research. The zwitterionic aza-Claisen rearrangement proved to be an effective and competitive complement to asymmetric electrophilic fluorination strategies and provides access to versatile synthetic intermediates with fluorine at the stereogenic centre.
dc.relation.ispartofBeilstein Journal of Organic Chemistryen
dc.rights© 2005 Tenza et al; licensee Beilstein-Institut. This is an Open Access article under the terms of the Creative Commons Attribution License (, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (
dc.subjectQD Chemistryen
dc.titleStereoselective alpha-fluoroamide and alpha-fluoro-gamma-lactone synthesis by an asymmetric zwitterionic aza-Claisen rearrangementen
dc.typeJournal articleen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews.Institute of Behavioural and Neural Sciencesen
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.description.statusPeer revieweden

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