Combined heterogeneous bio- and chemo-catalysis for dynamic kinetic resolution of (rac)-benzoin

dc.contributor.authorNieguth, R.
dc.contributor.authorten Dam, J.
dc.contributor.authorPetrenz, A.
dc.contributor.authorRamanathan, A.
dc.contributor.authorHanefeld, U.
dc.contributor.authorAnsorge-Schumacher, M. B.
dc.date.accessioned2016-06-21T08:29:22Z
dc.date.available2016-06-21T08:29:22Z
dc.date.issued2014
dc.description.abstractDynamic kinetic resolution (DKR) of racemic starting material is a promising route to optically pure (S)-benzoin (2-hydroxy-1,2-di(phenyl)ethanone) and various symmetrical and unsymmetrical derivatives thereof. Here, this route was advanced towards technical scale synthesis using the basic (rac)-benzoin as model system. The reaction employed stereoselective transesterification of (S)-benzoin with lipase TL® from Pseudomonas stutzeri and racemization of (R)-benzoin with Metal-TUD-1, a metal-associated acidic meso-porous silicate, in pure organic solvent. Enzyme performance was improved by immobilization on Accurel MP1001 (yielding Acc-LipTL), and Zr-TUD-1 (Si/Zr = 25) was identified as most effective racemization catalyst. Compatibility in solvent and temperature dependency enabled performance in only one pot. DKR in toluene at 50 °C yielded conversions above 98% and an ee of >97% in only five hours. Stability of Acc-LipTL was further improved with polyethylene imine and the reaction system was then reused in five cycles, retaining a conversion of >99% and a product-ee of >98%. On a semi-preparative scale, the isolated yield of enantiopure (S)-benzoin butyrate was >98%. Thus, the system provides a good basis for synthesis of enantiopure benzoin, and potentially a broader range of aromatic α-hydroxy ketones.en
dc.identifier.eissn2046-2069
dc.identifier.urihttp://depositonce.tu-berlin.de/handle/11303/5578
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-5207
dc.language.isoen
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.titleCombined heterogeneous bio- and chemo-catalysis for dynamic kinetic resolution of (rac)-benzoinen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/c4ra06751g
dcterms.bibliographicCitation.issue85
dcterms.bibliographicCitation.journaltitleRSC Advances : an international journal to further the chemical sciencesen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistryde
dcterms.bibliographicCitation.originalpublisherplaceCambridgede
dcterms.bibliographicCitation.pageend45503
dcterms.bibliographicCitation.pagestart45495
dcterms.bibliographicCitation.volume4
tub.accessrights.dnbfree
tub.affiliationFak. 2 Mathematik und Naturwissenschaften>Inst. Chemie>FG Technische Chemiede
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Technische Chemiede
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlin
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