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dc.contributor.authorArokianathar, Jude N.
dc.contributor.authorFrost, Aileen B.
dc.contributor.authorSlawin, Alexandra M. Z.
dc.contributor.authorStead, Darren
dc.contributor.authorSmith, Andrew D.
dc.date.accessioned2018-12-12T00:36:28Z
dc.date.available2018-12-12T00:36:28Z
dc.date.issued2018-02-02
dc.identifier.citationArokianathar , J N , Frost , A B , Slawin , A M Z , Stead , D & Smith , A D 2018 , ' Isothiourea-catalyzed enantioselective addition of 4-nitrophenyl esters to iminium ions ' , ACS Catalysis , vol. 8 , no. 2 , pp. 1153-1160 . https://doi.org/10.1021/acscatal.7b02697en
dc.identifier.issn2155-5435
dc.identifier.otherPURE: 251746585
dc.identifier.otherPURE UUID: 67097555-a22d-49a2-b998-ac79617e7221
dc.identifier.otherScopus: 85041483624
dc.identifier.otherORCID: /0000-0002-2104-7313/work/39714949
dc.identifier.otherORCID: /0000-0002-9527-6418/work/56861715
dc.identifier.otherWOS: 000424735000051
dc.identifier.urihttp://hdl.handle.net/10023/16668
dc.descriptionThe authors thank AstraZeneca and the EPSRC (grant codes EP/M506631/1; J.N.A. and EP/J018139/1; A.B.F.) 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. A.D.S. thanks the Royal Society for a Wolfson Research Merit Award.en
dc.description.abstractIsothioureas catalyze the enantioselective addition of 4-nitrophenyl esters to tetrahydroisoquinoline-derived iminium ions. 4-Nitrophenoxide, generated in situ from initial N-acylation of the isothiourea by the 4-nitrophenyl ester, is used to facilitate catalyst turnover in this reaction process. Optimization showed that 4-nitrophenyl esters give the best reactivity in this protocol over a range of alternative aryl esters, with the observed enantioselectivity markedly dependent upon the nature of the iminium counteri-on. Highest yields and enantioselectivity were obtained using iminium bromide ions generated in situ via photoredox catalysis using BrCCl3 and Ru(bpy)3Cl2 (0.5 mol%) and commercially available tetramisole (5 mol%) as the Lewis base catalyst. The scope and limitations of this procedure was developed, giving the desired β-amino amide products in up to 96% yield, 79:21 dr and ermajor (2R,1′S) 99.5:0.5.
dc.language.isoeng
dc.relation.ispartofACS Catalysisen
dc.rightsCopyright © 2017 American Chemical Society. This work has been made available online in accordance with the publisher’s policies. This is the author created accepted version manuscript following peer review and as such may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1021/acscatal.7b02697en
dc.subjectQD Chemistryen
dc.subjectDASen
dc.subject.lccQDen
dc.titleIsothiourea-catalyzed enantioselective addition of 4-nitrophenyl esters to iminium ionsen
dc.typeJournal articleen
dc.description.versionPostprinten
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.identifier.doihttps://doi.org/10.1021/acscatal.7b02697
dc.description.statusPeer revieweden
dc.date.embargoedUntil2018-12-12


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