{"data":{"id":"10.6084/m9.figshare.c.3911929","type":"dois","attributes":{"doi":"10.6084/m9.figshare.c.3911929","prefix":"10.6084","suffix":"m9.figshare.c.3911929","identifiers":[],"alternateIdentifiers":[],"creators":[{"name":"Yacob, Sara","nameType":"Personal","givenName":"Sara","familyName":"Yacob","affiliation":[],"nameIdentifiers":[]},{"name":"Caulfield, Michael J.","nameType":"Personal","givenName":"Michael J.","familyName":"Caulfield","affiliation":[],"nameIdentifiers":[]},{"name":"Barckholtz, Timothy A.","nameType":"Personal","givenName":"Timothy A.","familyName":"Barckholtz","affiliation":[],"nameIdentifiers":[]}],"titles":[{"title":"Supplementary material from \"Partial oxidation of alkanes by dioxiranes formed \u003ci\u003ein situ\u003c/i\u003e at low temperature\""}],"publisher":"Figshare","container":{},"publicationYear":2017,"subjects":[{"subject":"Organic Chemistry"},{"subject":"FOS: Chemical sciences","schemeUri":"http://www.oecd.org/science/inno/38235147.pdf","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"90499 Chemical Engineering not elsewhere classified","subjectScheme":"FOR"},{"subject":"FOS: Chemical engineering","schemeUri":"http://www.oecd.org/science/inno/38235147.pdf","subjectScheme":"Fields of Science and Technology (FOS)"}],"contributors":[],"dates":[{"date":"2017-10-24","dateType":"Created"},{"date":"2017-10-24","dateType":"Updated"},{"date":"2017","dateType":"Issued"}],"language":null,"types":{"ris":"GEN","bibtex":"misc","citeproc":"article","schemaOrg":"Collection","resourceType":"Collection","resourceTypeGeneral":"Collection"},"relatedIdentifiers":[{"relationType":"IsSupplementTo","relatedIdentifier":"10.1098/rsta.2017.0055","relatedIdentifierType":"DOI"}],"relatedItems":[],"sizes":[],"formats":[],"version":null,"rightsList":[{"rights":"CC BY 4.0","rightsUri":"https://creativecommons.org/licenses/by/4.0"}],"descriptions":[{"description":"Partial oxidation catalysts capable of efficiently operating at low temperatures may limit the over-oxidation of alkane substrates and thereby improve selectivity. This work focuses on examining alkane oxidation using completely metal-free organocatalysts, dioxiranes. Dioxiranes employed here are synthesized by oxidation of a ketone using a terminal oxidant, such as hydrogen peroxide. Our work generates the dioxirane \u003ci\u003ein situ\u003c/i\u003e, so that the process can be catalytic with respect to the ketone. To date, we have demonstrated selective partial oxidation of adamantane using ketone catalysts resulting in yields upwards of 60% towards 1-adamantanol with greater than 99% selectivity. Furthermore, we have demonstrated that changing the electrophilic character of the ketone R groups to contain more electron-donating ligands facilitates the dioxirane ring formation and improves overall oxidation yields. Isotopic labelling studies using H\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e18\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003e show the preferential incorporation of an \u003csup\u003e18\u003c/sup\u003eO label into the parent ketone, providing evidence for dioxirane intermediate formed \u003ci\u003ein situ\u003c/i\u003e. The isotopic labelling studies, along with solvent effect studies, suggest the formation of peracetic acid as a reactive intermediate.","descriptionType":"Abstract"}],"geoLocations":[],"fundingReferences":[],"xml":"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","url":"https://figshare.com/collections/Supplementary_material_from_Partial_oxidation_of_alkanes_by_dioxiranes_formed_i_in_situ_i_at_low_temperature_/3911929","contentUrl":null,"metadataVersion":2,"schemaVersion":"http://datacite.org/schema/kernel-4","source":"api","isActive":true,"state":"findable","reason":null,"viewCount":0,"viewsOverTime":[],"downloadCount":0,"downloadsOverTime":[],"referenceCount":1,"citationCount":0,"citationsOverTime":[],"partCount":0,"partOfCount":0,"versionCount":0,"versionOfCount":0,"created":"2017-10-24T13:22:47.000Z","registered":"2017-10-24T13:22:47.000Z","published":"2017","updated":"2024-12-19T08:12:05.000Z"},"relationships":{"client":{"data":{"id":"figshare.ars","type":"clients"}},"provider":{"data":{"id":"otjm","type":"providers"}},"media":{"data":{"id":"10.6084/m9.figshare.c.3911929","type":"media"}},"references":{"data":[{"id":"10.1098/rsta.2017.0055","type":"dois"}]},"citations":{"data":[]},"parts":{"data":[]},"partOf":{"data":[]},"versions":{"data":[]},"versionOf":{"data":[]}}}}