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dc.contributor.authorBarrios Antunez, Diego-Javier
dc.contributor.authorGreenhalgh, Mark D.
dc.contributor.authorBrueckner, Alexander C.
dc.contributor.authorWalden, Daniel M.
dc.contributor.authorElías-Rodríguez, Pilar
dc.contributor.authorRoberts, Patrick
dc.contributor.authorYoung, Benjamin G.
dc.contributor.authorWest, Thomas H.
dc.contributor.authorSlawin, Alexandra M. Z.
dc.contributor.authorCheong, Paul Ha-Yeon
dc.contributor.authorSmith, Andrew D.
dc.identifier.citationBarrios Antunez , D-J , Greenhalgh , M D , Brueckner , A C , Walden , D M , Elías-Rodríguez , P , Roberts , P , Young , B G , West , T H , Slawin , A M Z , Cheong , P H-Y & Smith , A D 2019 , ' Catalytic enantioselective synthesis of perfluoroalkyl-substituted β-lactones via a concerted asynchronous [2+2] cycloaddition : a synthetic and computational study ' , Chemical Science , vol. 10 , no. 24 , pp. 6162-6173 .
dc.identifier.otherPURE: 258834859
dc.identifier.otherPURE UUID: 5b5a8da5-cade-4ce1-8a40-644f1b92fe6e
dc.identifier.otherORCID: /0000-0002-2104-7313/work/57088422
dc.identifier.otherORCID: /0000-0002-9527-6418/work/57088431
dc.identifier.otherScopus: 85067662767
dc.identifier.otherWOS: 000472557100011
dc.descriptionThe research leading to these results (D.-J.B.A., T.H.W., A.D.S.) has received funding from the ERC under the European Union’s Seventh Framework Programme (FP7/2007-2013)/E.R.C. Grant Agreement No. 279850. A.D.S. thanks the Royal Society for a Wolfson Research Merit Award. We also thank the EPSRC UK National Mass Spectrometry Facility at Swansea University. P.H.Y.C. is the Bert and Emelyn Christensen professor of OSU, and gratefully acknowledges financial support from the Vicki & Patrick F. Stone family. P.H.Y.C., A.C.B., D.M.W. and B.G.Y. gratefully acknowledge support from the National Science Foundation (NSF CHE-1352663) and the computing infrastructure in part provided by the NSF Phase-2 CCI, Center for Sustainable Materials Chemistry (NSF CHE-1102637).en
dc.description.abstractThe enantioselective preparation of a range of perfluoroalkyl-substituted β-lactones through an isothiourea (HyperBTM) catalysed reaction using symmetric anhydrides as ammonium enolate precursors and perfluoroalkylketones (RF = CF3, C2F5, C4F9) is reported. Following optimisation, high diastereo- and enantioselectivty was observed for β-lactone formation using C2F5- and C4F9-substituted ketones at room temperature (26 examples, up to > 95:5 dr and > 99:1 er), whilst −78 ˚C was necessary for optimal dr and er with CF3-substituted ketones (11 examples, up to > 95:5 dr and > 99:1 er). Derivatisation of the β-lactones through ring-opening, as well as a two-step conversion to give perfluoroalkyl-substituted oxetanes, is demonstrated without loss of stereochemical integrity. Density functional theory computations, alongside 13C natural abundance KIE studies, have been used to probe the reaction mechanism with a concerted asynchronous [2 + 2]-cycloaddition pathway favoured over a stepwise aldol-lactonisation process.
dc.relation.ispartofChemical Scienceen
dc.rightsCopyright © 2019 The Author(s). Open Access Article. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.en
dc.subjectQD Chemistryen
dc.titleCatalytic enantioselective synthesis of perfluoroalkyl-substituted β-lactones via a concerted asynchronous [2+2] cycloaddition : a synthetic and computational studyen
dc.typeJournal articleen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.contributor.institutionUniversity of St Andrews.Biomedical Sciences Research Complexen
dc.description.statusPeer revieweden

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