{"data":{"id":"10.6084/m9.figshare.c.3911929.v1","type":"dois","attributes":{"doi":"10.6084/m9.figshare.c.3911929.v1","prefix":"10.6084","suffix":"m9.figshare.c.3911929.v1","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"},{"relationType":"IsIdenticalTo","relatedIdentifier":"10.6084/m9.figshare.c.3911929","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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