Mechanistic investigation into the C(sp3)-H acetoxylation of morpholinones.

Simple item page
cam.issuedOnline2018-10
dc.contributor.authorBuettner, Cornelia S
dc.contributor.authorWillcox, Darren
dc.contributor.authorChappell, Ben GN
dc.contributor.authorGaunt, Matthew J
dc.contributor.orcidWillcox, Darren [0000-0002-1396-7734]
dc.contributor.orcidGaunt, Matthew J [0000-0002-7214-608X]
dc.date.accessioned2018-11-22T00:31:08Z
dc.date.available2018-11-22T00:31:08Z
dc.date.issued2019-01-07
dc.description.abstractThe study of a selective palladium(ii)-catalyzed C(sp3)-H acetoxylation reaction on a class of cyclic alkyl amines is reported. Computational modelling and kinetic studies were used to provide support for a mechanism involving selective C-O bond formation from a γ-aminoalkyl-Pd(iv) intermediate. The C-O bond forming step was computed to occur by a dissociative ionization mechanism followed by an SN2 process involving external acetate attack at the C-Pd(iv) bond. This pathway was computed to be of lowest energy with no competing C-N products observed. Additionally, with a few modifications to reaction conditions, preliminary studies showed that this process could be rendered enantioselective in the presence of a non-racemic BINOL-phosphoric acid.
dc.format.mediumElectronic-eCollection
dc.identifier.doi10.17863/CAM.32963
dc.identifier.eissn2041-6539
dc.identifier.issn2041-6520
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/285609
dc.languageeng
dc.publisherRoyal Society of Chemistry (RSC)
dc.publisher.urlhttp://dx.doi.org/10.1039/c8sc03434f
dc.rightsAttribution 4.0 International
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subject3405 Organic Chemistry
dc.subject34 Chemical Sciences
dc.titleMechanistic investigation into the C(sp3)-H acetoxylation of morpholinones.
dc.typeArticle
dcterms.dateAccepted2018-09-28
prism.endingPage89
prism.issueIdentifier1
prism.publicationDate2019
prism.publicationNameChem Sci
prism.startingPage83
prism.volume10
pubs.funder-project-idEngineering and Physical Sciences Research Council (EP/N031792/1)
rioxxterms.licenseref.startdate2019-01
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserved
rioxxterms.typeJournal Article/Review
rioxxterms.versionVoR
rioxxterms.versionofrecord10.1039/c8sc03434f
Files
Original bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
c8sc03434f.pdf
Size:
1.05 MB
Format:
Adobe Portable Document Format
Description:
Published version
Licence
https://creativecommons.org/licenses/by/4.0/
Download
License bundle
Now showing 1 - 1 of 1
No Thumbnail Available
Name:
DepositLicenceAgreementv2.1.pdf
Size:
150.9 KB
Format:
Adobe Portable Document Format
Download
Collections
Cambridge University Research Outputs