{"data":{"id":"10.6084/m9.figshare.777773","type":"dois","attributes":{"doi":"10.6084/m9.figshare.777773","prefix":"10.6084","suffix":"m9.figshare.777773","identifiers":[],"alternateIdentifiers":[],"creators":[{"name":"Rzepa, Henry S.","nameType":"Personal","givenName":"Henry S.","familyName":"Rzepa","affiliation":[],"nameIdentifiers":[{"schemeUri":"https://orcid.org","nameIdentifier":"https://orcid.org/0000-0002-8635-8390","nameIdentifierScheme":"ORCID"}]},{"name":"Cherblanc, Fanny L.","nameType":"Personal","givenName":"Fanny L.","familyName":"Cherblanc","affiliation":[],"nameIdentifiers":[]},{"name":"Herrebout, Wouter A.","nameType":"Personal","givenName":"Wouter A.","familyName":"Herrebout","affiliation":[],"nameIdentifiers":[]},{"name":"Bultinck, Patrick","nameType":"Personal","givenName":"Patrick","familyName":"Bultinck","affiliation":[],"nameIdentifiers":[]},{"name":"Fuchter, Matthew J.","nameType":"Personal","givenName":"Matthew J.","familyName":"Fuchter","affiliation":[],"nameIdentifiers":[]},{"name":"Ya-Pei Lo","affiliation":[],"nameIdentifiers":[]}],"titles":[{"title":"Mechanistic and chiroptical studies on the desulfurization of epidithiodioxopiperazines reveal universal retention of configuration at the bridgehead carbon atoms."}],"publisher":"figshare","container":{},"publicationYear":2013,"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":"FOS: Chemical sciences","subjectScheme":"Fields of Science and Technology (FOS)"},{"subject":"Stereochemistry"},{"subject":"NMR Spectroscopy"}],"contributors":[],"dates":[{"date":"2013-08-21","dateType":"Created"},{"date":"2015-12-02","dateType":"Updated"},{"date":"2013","dateType":"Issued"}],"language":null,"types":{"ris":"DATA","bibtex":"misc","citeproc":"dataset","schemaOrg":"Dataset","resourceType":"Dataset","resourceTypeGeneral":"Dataset"},"relatedIdentifiers":[],"relatedItems":[],"sizes":["754122 Bytes"],"formats":[],"version":null,"rightsList":[{"rights":"Creative Commons Attribution 4.0 International","rightsUri":"https://creativecommons.org/licenses/by/4.0/legalcode","schemeUri":"https://spdx.org/licenses/","rightsIdentifier":"cc-by-4.0","rightsIdentifierScheme":"SPDX"}],"descriptions":[{"description":"2,3,10,10-Tetramethyl-2,3-dihydro-1H-3,10a-epithiopyrazino[1,2-a]indole-1,4(10H)-dione (\u003cstrong\u003e8\u003c/strong\u003e). To a solution of gliotoxin analogue (7, 33 mg, 0.10 mmol) in dioxane (8 mL) was added PPh3 (33 mg, 0.16 mmol) and the resulting mixture was stirred overnight at room temperature. The solvent was then re-moved under reduced pressure and the pink residue was purified by column chromatography [PEEtOAc (100:0 to 95:5)] to afford a colorless oil (19 mg, 64%) which was recrystallized from CH2Cl2 to give a white solid: m.p. 58 60 C; IR (neat) 1720, 1456, 1387, 1288, 1134 cm-1; 1H NMR (400 MHz, CDCl3) 8.54 (app-d, J = 7.8 Hz, 1H), 7.25 (td, J = 7.8, 1.0 Hz, 1H), 7.20 (dd, J = 7.8, 1.0 Hz, 1H), 7.13 (td, J = 7.8, 1.0 Hz, 1H), 2.96 (s, 3H), 1.83 (s, 3H), 1.75 (s, 3H), 1.48 (s, 3H); 13C NMR (100 MHz, CDCl3) 172.5, 172.0, 139.7, 138.1, 128.1, 124.7, 122.4, 113.6, 86.6, 75.1, 43.5, 27.2, 26.3, 25.7, 13.3; MS (CI) m/z 289 (M+H)+, 306 (M+NH4)+; HRMS (CI) m/z calcd for C15H17N2O2S [(M+H)+] 289.1011, found: 289.1026. The obtained enantiomers could be separated by chiral HPLC (OD+ semiprep column, Hexane : Isopropanol, 90:10): First peak: [α]25D -47.5 (c 1.12, CH2Cl2), Second peak: [α]25D +34.4 (c 1.12, CH2Cl2).","descriptionType":"Abstract"}],"geoLocations":[],"fundingReferences":[],"xml":"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","url":"https://figshare.com/articles/dataset/Mechanistic_and_chiroptical_studies_on_the_desulfurization_of_epidithiodioxopiperazines_reveal_universal_retention_of_configuration_at_the_bridgehead_carbon_atoms_/777773","contentUrl":null,"metadataVersion":2,"schemaVersion":"http://datacite.org/schema/kernel-4","source":"mds","isActive":true,"state":"findable","reason":null,"viewCount":0,"viewsOverTime":[],"downloadCount":0,"downloadsOverTime":[],"referenceCount":0,"citationCount":1,"citationsOverTime":[{"year":"2025","total":1}],"partCount":0,"partOfCount":0,"versionCount":0,"versionOfCount":0,"created":"2013-08-21T12:15:06.000Z","registered":"2013-08-21T12:15:08.000Z","published":"2013","updated":"2020-09-05T01:33:36.000Z"},"relationships":{"client":{"data":{"id":"figshare.ars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