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dc.contributor.authorQu, Shen
dc.contributor.authorGreenhalgh, Mark D.
dc.contributor.authorSmith, Andrew D.
dc.date.accessioned2020-01-28T00:34:46Z
dc.date.available2020-01-28T00:34:46Z
dc.date.issued2019-01-28
dc.identifier.citationQu , S , Greenhalgh , M D & Smith , A D 2019 , ' Isothiourea-catalysed regioselective acylative kinetic resolution of axially chiral biaryl diols ' , Chemistry - A European Journal , vol. Early View . https://doi.org/10.1002/chem.201805631en
dc.identifier.issn0947-6539
dc.identifier.otherPURE: 256940786
dc.identifier.otherPURE UUID: 1c78cb5c-3cc1-4da6-9322-19c43c34f397
dc.identifier.otherScopus: 85060762235
dc.identifier.otherORCID: /0000-0002-2104-7313/work/51700113
dc.identifier.otherWOS: 000459323700023
dc.identifier.urihttps://hdl.handle.net/10023/19361
dc.descriptionThe research leading to these results has received funding from the ERC under the European Union's Seventh Framework Programme (FP7/2007-2013)/E.R.C. grant agreement n° 279850. The Chinese Scholarship Scheme and University of St Andrews are thanked for a CSC Scholarship (S.Q.). A.D.S. thanks the Royal Society for a Wolfson Research Merit Award.en
dc.description.abstractAn operationally‐simple isothiourea‐catalyzed acylative kinetic resolution of unprotected 1,1′‐biaryl‐2,2′‐diol derivatives has been developed to allow access to axially chiral compounds in highly enantioenriched form (s values up to 190). Investigation of the reaction scope and limitations provided three key observations: i) the diol motif of the substrate was essential for good conversion and high s values; ii) the use of an α,α‐disubstituted mixed anhydride (2,2‐diphenylacetic pivalic anhydride) was critical to minimize diacylation and give high selectivity; iii) the presence of substituents in the 3,3′‐positions of the diol hindered effective acylation. This final observation was exploited for the highly regioselective acylative kinetic resolution of unsymmetrical biaryl diol substrates bearing a single 3‐substituent. Based on the key observations identified, acylation transition state models have been proposed to explain the atropselectivity of this kinetic resolution.
dc.language.isoeng
dc.relation.ispartofChemistry - A European Journalen
dc.rightsCopyright © 2019 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim. 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/10.1002/chem.201805631en
dc.subjectBiarylen
dc.subjectKinetic resolutionen
dc.subjectEnantioselectivityen
dc.subjectRegioselectivityen
dc.subjectAxial chiralityen
dc.subjectQD Chemistryen
dc.subjectDASen
dc.subject.lccQDen
dc.titleIsothiourea-catalysed regioselective acylative kinetic resolution of axially chiral biaryl diolsen
dc.typeJournal articleen
dc.contributor.sponsorEuropean Commissionen
dc.contributor.sponsorThe Royal Societyen
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/10.1002/chem.201805631
dc.description.statusPeer revieweden
dc.date.embargoedUntil2020-01-28
dc.identifier.grantnumberN/Aen
dc.identifier.grantnumberWM140071en


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