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dc.creatorBjelaković, Mira
dc.creatorKrstić, Natalija
dc.creatorMilić, Dragana
dc.creatorKop, Tatjana
dc.creatorRobeyns, Koen
dc.creatorPavlovic, Vladimir D.
dc.date.accessioned2019-01-30T17:32:50Z
dc.date.available2019-01-30T17:32:50Z
dc.date.issued2012
dc.identifier.issn0040-4020
dc.identifier.urihttp://cer.ihtm.bg.ac.rs/handle/123456789/1114
dc.description.abstractThe present study is concerned with the oxidative behaviour of unsaturated and epoxy 5-oxo-5,10-secosteroids in the presence of m-CPBA or TFAA-UHP as oxidants in order to investigate potential parameters controlling the chemoselectivity and regioselectivity. In the study we discovered a striking difference in the chemical behaviour of stereoisomeric compounds, (Z)- and (E)-3 beta-acetoxy-5,10-secocholest-1(10)-en-5-ones, as well as 1S,10R- and 1R,10R-epoxides. The secoketones were oxidized with exclusively C-6 migration and Baeyer-Villiger rearrangement product formation, whereas their stereoisomers provided the ring-contracted products, without lactone formation. The preferred conformation of expanded and contracted rings was established by NOESY correlations. The structures of two obtained lactones were also confirmed by X-ray analysis. The mechanistic and stereochemical aspects of these transformations are discussed.en
dc.publisherPergamon-Elsevier Science Ltd, Oxford
dc.relationinfo:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172002/RS//
dc.rightsrestrictedAccess
dc.sourceTetrahedron
dc.subject5-Oxo-5,10-secosteroidsen
dc.subject5,10-Secosteroidal 5,6-lactonesen
dc.subjectm-CPBAen
dc.subjectTFAA-UHP reagenten
dc.subjectBaeyer-Villiger oxidationen
dc.titleOxidative 10-membered ring expansion and contraction of stereoisomeric 1(10)-unsaturated and 1,10-epoxy-5-oxo-5,10-secosteroids induced by peracidsen
dc.typearticle
dc.rights.licenseARR
dcterms.abstractБјелаковић, Мира; Коп, Татјана; Милиц, Драгана Р.; Павловиц, Владимир Д.; Крстић, Наталија; Робеyнс, Коен;
dc.citation.volume68
dc.citation.issue36
dc.citation.spage7479
dc.citation.epage7488
dc.citation.other68(36): 7479-7488
dc.citation.rankM22
dc.identifier.doi10.1016/j.tet.2012.06.024
dc.identifier.rcubConv_2835
dc.identifier.scopus2-s2.0-84864279987
dc.identifier.wos000307698100029
dc.type.versionpublishedVersion


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