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dc.contributor.authorPhipps, Roberten
dc.contributor.authorGolding, Williamen
dc.contributor.authorPearce-Higgins, Roberten
dc.date.accessioned2018-11-22T00:32:50Z
dc.date.available2018-11-22T00:32:50Z
dc.identifier.issn1520-5126
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/285676
dc.description.abstractControl of site-selectivity in chemical reactions that occur remote from existing functionality remains a major challenge in synthetic chemistry. We describe a strategy that enables three of the most commonly used cross-coupling processes to occur with high site-selectivity on dichloroarenes which bear acidic functional groups. We have achieved this by repurposing an established sulfonylated phosphine ligand to exploit its inherent bifunctionality. Mechanistic studies suggest that the sulfonate group engages in attractive electrostatic interactions with the associated cation of deprotonated substrate, guiding cross-coupling to the chloride at the arene meta-position. This counterintuitive combination of anionic ligand and anionic substrate demonstrates an alternative design principle when considering applying non-covalent interactions to direct catalysis.
dc.description.sponsorshipWe are grateful to AstraZeneca for PhD studentships through the AZ‐Cambridge PhD program (W.A.G. and R.P.), the Royal Society for a University Research Fellowship (R.J.P.), the EPSRC (EP/N005422/1) and the ERC (StG 757381).
dc.publisherAmerican Chemical Society (ACS)
dc.titleSite-Selective Cross-Coupling of Remote Chlorides Enabled by Electrostatically-Directed Palladium Catalysisen
dc.typeArticle
prism.publicationNameJournal of the American Chemical Societyen
dc.identifier.doi10.17863/CAM.33028
dcterms.dateAccepted2018-10-08en
rioxxterms.versionofrecord10.1021/jacs.8b08686en
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserveden
rioxxterms.licenseref.startdate2018-10-08en
dc.contributor.orcidPhipps, Robert [0000-0002-7383-5469]
dc.contributor.orcidGolding, William [0000-0001-6956-4961]
dc.identifier.eissn1520-5126
rioxxterms.typeJournal Article/Reviewen
pubs.funder-project-idEPSRC (EP/N005422/1)
pubs.funder-project-idRoyal Society (uf130004)
pubs.funder-project-idEuropean Commission Horizon 2020 (H2020) ERC (757381)
cam.issuedOnline2018-10-08en
rioxxterms.freetoread.startdate2019-10-08


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