Mechanistic investigation into the C(sp3)-H acetoxylation of morpholinones.
| cam.issuedOnline | 2018-10 | |
| dc.contributor.author | Buettner, Cornelia S | |
| dc.contributor.author | Willcox, Darren | |
| dc.contributor.author | Chappell, Ben GN | |
| dc.contributor.author | Gaunt, Matthew J | |
| dc.contributor.orcid | Willcox, Darren [0000-0002-1396-7734] | |
| dc.contributor.orcid | Gaunt, Matthew J [0000-0002-7214-608X] | |
| dc.date.accessioned | 2018-11-22T00:31:08Z | |
| dc.date.available | 2018-11-22T00:31:08Z | |
| dc.date.issued | 2019-01-07 | |
| dc.description.abstract | The 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.medium | Electronic-eCollection | |
| dc.identifier.doi | 10.17863/CAM.32963 | |
| dc.identifier.eissn | 2041-6539 | |
| dc.identifier.issn | 2041-6520 | |
| dc.identifier.uri | https://www.repository.cam.ac.uk/handle/1810/285609 | |
| dc.language | eng | |
| dc.language.iso | eng | |
| dc.publisher | Royal Society of Chemistry (RSC) | |
| dc.publisher.url | http://dx.doi.org/10.1039/c8sc03434f | |
| dc.rights | Attribution 4.0 International | |
| dc.rights.uri | https://creativecommons.org/licenses/by/4.0/ | |
| dc.subject | 3405 Organic Chemistry | |
| dc.subject | 34 Chemical Sciences | |
| dc.title | Mechanistic investigation into the C(sp3)-H acetoxylation of morpholinones. | |
| dc.type | Article | |
| dcterms.dateAccepted | 2018-09-28 | |
| prism.endingPage | 89 | |
| prism.issueIdentifier | 1 | |
| prism.publicationDate | 2019 | |
| prism.publicationName | Chem Sci | |
| prism.startingPage | 83 | |
| prism.volume | 10 | |
| pubs.funder-project-id | Engineering and Physical Sciences Research Council (EP/N031792/1) | |
| rioxxterms.licenseref.startdate | 2019-01 | |
| rioxxterms.licenseref.uri | http://www.rioxx.net/licenses/all-rights-reserved | |
| rioxxterms.type | Journal Article/Review | |
| rioxxterms.version | VoR | |
| rioxxterms.versionofrecord | 10.1039/c8sc03434f |
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