Combined heterogeneous bio- and chemo-catalysis for dynamic kinetic resolution of (rac)-benzoin
| dc.contributor.author | Nieguth, R. | |
| dc.contributor.author | ten Dam, J. | |
| dc.contributor.author | Petrenz, A. | |
| dc.contributor.author | Ramanathan, A. | |
| dc.contributor.author | Hanefeld, U. | |
| dc.contributor.author | Ansorge-Schumacher, M. B. | |
| dc.date.accessioned | 2016-06-21T08:29:22Z | |
| dc.date.available | 2016-06-21T08:29:22Z | |
| dc.date.issued | 2014 | |
| dc.description.abstract | Dynamic 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.eissn | 2046-2069 | |
| dc.identifier.uri | https://depositonce.tu-berlin.de/handle/11303/5578 | |
| dc.identifier.uri | http://dx.doi.org/10.14279/depositonce-5207 | |
| dc.language.iso | en | |
| dc.rights.uri | https://creativecommons.org/licenses/by/3.0/ | |
| dc.subject.ddc | 540 Chemie und zugeordnete Wissenschaften | de |
| dc.title | Combined heterogeneous bio- and chemo-catalysis for dynamic kinetic resolution of (rac)-benzoin | en |
| dc.type | Article | en |
| dc.type.version | publishedVersion | en |
| dcterms.bibliographicCitation.doi | 10.1039/c4ra06751g | |
| dcterms.bibliographicCitation.issue | 85 | |
| dcterms.bibliographicCitation.journaltitle | RSC Advances : an international journal to further the chemical sciences | en |
| dcterms.bibliographicCitation.originalpublishername | Royal Society of Chemistry | de |
| dcterms.bibliographicCitation.originalpublisherplace | Cambridge | de |
| dcterms.bibliographicCitation.pageend | 45503 | |
| dcterms.bibliographicCitation.pagestart | 45495 | |
| dcterms.bibliographicCitation.volume | 4 | |
| tub.accessrights.dnb | free | |
| tub.affiliation | Fak. 2 Mathematik und Naturwissenschaften::Inst. Chemie::FG Technische Chemie | de |
| tub.affiliation.faculty | Fak. 2 Mathematik und Naturwissenschaften | de |
| tub.affiliation.group | FG Technische Chemie | de |
| tub.affiliation.institute | Inst. Chemie | de |
| tub.publisher.universityorinstitution | Technische Universität Berlin |
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