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dc.contributor.authorPeel, Andrew J
dc.contributor.authorTerzopoulos, Alexandros
dc.contributor.authorJethwa, Rajesh B
dc.contributor.authorChoudhury, Dipanjana
dc.contributor.authorNiu, Hao-Che
dc.contributor.authorBond, Andrew D
dc.contributor.authorSlaughter, Jonathan
dc.contributor.authorWright, Dominic S
dc.date.accessioned2022-07-04T01:02:30Z
dc.date.available2022-07-04T01:02:30Z
dc.date.issued2022-05-11
dc.identifier.issn2041-6520
dc.identifier.otherPMC9093139
dc.identifier.other35655560
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/338724
dc.description.abstractMethods for measuring enantiomeric excess (ee) of organic molecules by NMR spectroscopy provide rapid analysis using a standard technique that is readily available. Commonly this is accomplished by chiral derivatisation of the detector molecule (producing a chiral derivatisation agent, CDA), which is reacted with the mixture of enantiomers under investigation. However, these CDAs have almost exclusively been based on carbon frameworks, which are generally costly and/or difficult to prepare. In this work, a methodology based on the readily prepared inorganic cyclodiphosph(iii)azane CDA ClP(μ-N t Bu)2POBorn (Born = endo-(1S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl) is shown to be highly effective in the measurement of ee's of chiral amines, involving in situ reaction of the chiral amines (R*NH2) with the P-Cl bond of the CDA followed by quaternization of the phosphorus framework with methyl iodide. This results in sharp 31P NMR signals with distinct chemical shift differences between the diastereomers that are formed, which can be used to obtain the ee directly by integration. Spectroscopic, X-ray structural and DFT studies suggest that the NMR chemical shift differences between diastereomers is steric in origin, with the sharpness of these signals resulting from conformational locking of the bornyl group relative to the P2N2 ring induced by the presence of the P(v)-bonded amino group (R*NH). This study showcases cheap inorganic phosphazane CDAs as simple alternatives to organic variants for the rapid determination of ee.
dc.languageeng
dc.publisherRoyal Society of Chemistry (RSC)
dc.rightsAttribution 4.0 International
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.sourceessn: 2041-6539
dc.sourcenlmid: 101545951
dc.titleA chiral phosphazane reagent strategy for the determination of enantiomeric excess of amines.
dc.typeArticle
dc.date.updated2022-07-04T01:02:30Z
prism.endingPage5412
prism.issueIdentifier18
prism.publicationNameChem Sci
prism.startingPage5398
prism.volume13
dc.identifier.doi10.17863/CAM.86137
dcterms.dateAccepted2022-04-12
rioxxterms.versionofrecord10.1039/d2sc01692c
rioxxterms.versionVoR
rioxxterms.licenseref.urihttps://creativecommons.org/licenses/by/4.0/
dc.contributor.orcidJethwa, Rajesh B [0000-0002-0404-4356]
dc.contributor.orcidBond, Andrew D [0000-0002-1744-0489]
dc.contributor.orcidSlaughter, Jonathan [0000-0002-6401-8547]
dc.contributor.orcidWright, Dominic S [0000-0002-9952-3877]
dc.identifier.eissn2041-6539
pubs.funder-project-idEngineering and Physical Sciences Research Council (EP/R511870/1)
cam.issuedOnline2022-04-25


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Attribution 4.0 International
Except where otherwise noted, this item's licence is described as Attribution 4.0 International