Mild reductive rearrangement of oximes and oxime ethers to secondary amines with hydrosilanes catalyzed by B(C6F5)3

dc.contributor.authorFang, Huaquan
dc.contributor.authorWang, Guoqiang
dc.contributor.authorOestreich, Martin
dc.date.accessioned2021-12-29T13:15:18Z
dc.date.available2021-12-29T13:15:18Z
dc.date.issued2021-04-01
dc.description.abstractThe strong boron Lewis acid tris(pentafluorophenyl)borane, B(C6F5)3, has been found to catalyze the reductive rearrangement of oximes and their ether derivatives at room temperature with hydrosilanes as the reducing agents. Cyclic substrates undergo ring enlargement, and the secondary amine products are generally formed in good yields. Control experiments combined with a DFT computational analysis of the reaction mechanism suggest that there are three energetically accessible reaction pathways (paths A–C), either or not involving hydroxylamine derivatives. Paths A and B proceed through the intermediacy of a common N,O-bissilylated hydroxylamine, and the ring-expanding rearrangement yields an iminium ion. With no intermediate at the hydroxylamine oxidation level (path C), the reaction mechanism resembles that of the Beckmann rearrangement where an O-silylated oxime converts into a nitrilium ion. The reduction–rearrangement sequence (paths A and B) is slightly preferred over the rearrangement–reduction order of events (path C), especially at ambient temperature.en
dc.description.sponsorshipTU Berlin, Open-Access-Mittel – 2021en
dc.identifier.eissn2052-4129
dc.identifier.issn2052-4110
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/16024
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-14798
dc.language.isoenen
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/en
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.subject.othercatalysisen
dc.subject.otherreactionen
dc.subject.otherreductive rearrangementen
dc.subject.otheroximeen
dc.subject.otheroxime ethersen
dc.titleMild reductive rearrangement of oximes and oxime ethers to secondary amines with hydrosilanes catalyzed by B(C6F5)3en
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/d1qo00251aen
dcterms.bibliographicCitation.issue13en
dcterms.bibliographicCitation.journaltitleOrganic Chemistry Frontiersen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistry (RSC)en
dcterms.bibliographicCitation.originalpublisherplaceCambridgeen
dcterms.bibliographicCitation.pageend3285en
dcterms.bibliographicCitation.pagestart3280en
dcterms.bibliographicCitation.volume8en
tub.accessrights.dnbfreeen
tub.affiliationFak. 2 Mathematik und Naturwissenschaften>Inst. Chemie>FG Organische Chemie / Synthese und Katalysede
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Organische Chemie / Synthese und Katalysede
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlinen
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