Desymmetrization by asymmetric copper-catalyzed intramolecular C–H insertion reactions of α-diazo-β-oxosulfones

dc.check.date2020-03-04
dc.check.infoAccess to this article is restricted until 12 months after publication by request of the publisher.en
dc.contributor.authorBrouder, Thomas A.
dc.contributor.authorSlattery, Catherine N.
dc.contributor.authorFord, Alan
dc.contributor.authorKhandavilli, Udaya Bhaskara Rao
dc.contributor.authorSkořepová, Eliška
dc.contributor.authorEccles, Kevin S.
dc.contributor.authorLusi, Matteo
dc.contributor.authorLawrence, Simon E.
dc.contributor.authorMaguire, Anita R.
dc.contributor.funderIrish Research Councilen
dc.contributor.funderIrish Research Council for Science, Engineering and Technologyen
dc.contributor.funderScience Foundation Irelanden
dc.contributor.funderEuropean Regional Development Funden
dc.date.accessioned2019-04-29T08:54:36Z
dc.date.available2019-04-29T08:54:36Z
dc.date.issued2019-03-04
dc.date.updated2019-04-29T08:44:19Z
dc.description.abstractEffective desymmetrization in copper-catalyzed intramolecular C–H insertion reactions of α-diazo-β-oxosulfones in the formation of fused thiopyran dioxides is described for the first time. The use of a copper–bis(oxazoline)–NaBARF catalyst complex system leads to formation of the major thiopyran dioxide stereoisomer with up to 98:2 dr and up to 98% ee. The effect of varying the bis(oxazoline) ligand, copper salt, and site of C–H insertion on both diastereo- and enantioselectivities of these intramolecular C–H insertion reactions has been investigated. Similarly, desymmetrization in the formation of a fused cyclopentanone proceeds with up to 64% ee. These results represent the highest enantioselectivity reported to date in a copper-mediated desymmetrization through C–H insertion.en
dc.description.sponsorshipIrish Research Council (GOIPG/2015/3188);en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationBrouder, T. A., Slattery, C. N., Ford, A., Khandavilli, U. B. R., Skořepová, E., Eccles, K. S., Lusi, M., Lawrence, S. E. and Maguire, A. R. (2019) 'Desymmetrization by Asymmetric Copper-Catalyzed Intramolecular C–H Insertion Reactions of α-Diazo-β-oxosulfones', The Journal of Organic Chemistry, In Press. doi: 10.1021/acs.joc.8b03160en
dc.identifier.doi10.1021/acs.joc.8b03160en
dc.identifier.endpage52en
dc.identifier.issn0022-3263
dc.identifier.journaltitleThe Journal of Organic Chemistryen
dc.identifier.startpage1en
dc.identifier.urihttps://hdl.handle.net/10468/7812
dc.language.isoenen
dc.publisherAmerican Chemical Society, ACSen
dc.relation.projectinfo:eu-repo/grantAgreement/SFI/SFI Research Centres/12/RC/2275/IE/Synthesis and Solid State Pharmaceutical Centre (SSPC)/en
dc.relation.projectinfo:eu-repo/grantAgreement/SFI/SFI Research Infrastructure Programme/15/RI/3221/IE/Process Flow Spectroscopy (ProSpect); Advanced Reaction Understanding using Flow Nuclear Magnetic Resonance (NMR) and Infrared (IR) Spectroscopies, with On-Line Ultra-Performance Liquid Chromatography (UPLC) and Mass Spectrometry (MS)/en
dc.relation.urihttps://pubs.acs.org/doi/10.1021/acs.joc.8b03160
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Organic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.joc.8b03160en
dc.subjectCopper-catalyzeden
dc.subjectAsymmetricen
dc.subjectC–H insertionen
dc.subjectCopper-mediated desymmetrizationen
dc.titleDesymmetrization by asymmetric copper-catalyzed intramolecular C–H insertion reactions of α-diazo-β-oxosulfonesen
dc.typeArticle (peer-reviewed)en
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