دورية أكاديمية
Biphasic Bioelectrocatalytic Synthesis of Chiral β-Hydroxy Nitriles.
| العنوان: | Biphasic Bioelectrocatalytic Synthesis of Chiral β-Hydroxy Nitriles. |
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| المؤلفون: | Dong F; Department of Chemistry, University of Utah, 315 South 1400 East, RM 2020, Salt Lake City, Utah 84112, United States., Chen H; Department of Chemistry, University of Utah, 315 South 1400 East, RM 2020, Salt Lake City, Utah 84112, United States., Malapit CA; Department of Chemistry, University of Utah, 315 South 1400 East, RM 2020, Salt Lake City, Utah 84112, United States., Prater MB; Department of Chemistry, University of Utah, 315 South 1400 East, RM 2020, Salt Lake City, Utah 84112, United States., Li M; Department of Chemistry, University of Utah, 315 South 1400 East, RM 2020, Salt Lake City, Utah 84112, United States., Yuan M; Department of Chemistry, University of Utah, 315 South 1400 East, RM 2020, Salt Lake City, Utah 84112, United States., Lim K; Department of Chemistry, University of Utah, 315 South 1400 East, RM 2020, Salt Lake City, Utah 84112, United States., Minteer SD; Department of Chemistry, University of Utah, 315 South 1400 East, RM 2020, Salt Lake City, Utah 84112, United States. |
| المصدر: | Journal of the American Chemical Society [J Am Chem Soc] 2020 May 06; Vol. 142 (18), pp. 8374-8382. Date of Electronic Publication: 2020 Apr 27. |
| نوع المنشور: | Journal Article; Research Support, U.S. Gov't, Non-P.H.S. |
| اللغة: | English |
| بيانات الدورية: | Publisher: American Chemical Society Country of Publication: United States NLM ID: 7503056 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-5126 (Electronic) Linking ISSN: 00027863 NLM ISO Abbreviation: J Am Chem Soc Subsets: MEDLINE |
| أسماء مطبوعة: | Publication: Washington, DC : American Chemical Society Original Publication: Easton, Pa. [etc.] |
| مواضيع طبية MeSH: | Alcohol Dehydrogenase/*metabolism , Hydrolases/*metabolism , Nitriles/*metabolism, Alcohol Dehydrogenase/chemistry ; Biocatalysis ; Electrochemical Techniques ; Hydrolases/chemistry ; Molecular Structure ; Nitriles/chemistry |
| مستخلص: | Two obstacles limit the application of oxidoreductase-based asymmetric synthesis. One is the consumption of high stoichiometric amounts of reduced cofactor. The other is the low solubility of organic substrates, intermediates, and products in the aqueous phase. In order to address these two obstacles to oxidoreductase-based asymmetric synthesis, a biphasic bioelectrocatalytic system was constructed and applied. In this study, the preparation of chiral β-hydroxy nitriles catalyzed by alcohol dehydrogenase (AdhS) and halohydrin dehalogenase (HHDH) was investigated as a model bioelectrosynthesis, since they are high-value intermediates in statin synthesis. Diaphorase (DH) was immobilized by a cobaltocene-modified poly(allylamine) redox polymer on the electrode surface (DH/ Cc -PAA bioelectrode) to achieve effective bioelectrocatalytic NADH regeneration. Since AdhS is a NAD-dependent dehydrogenase, the diaphorase-modified biocathode was used to regenerate NADH to support the conversion from ethyl 4-chloroacetoacetate (COBE) to ethyl ( S )-4-chloro-3-hydroxybutanoate (( S )-CHBE) catalyzed by AdhS. The addition of methyl tert -butyl ether (MTBE) as an organic phase not only increased the uploading of COBE but also prevented the spontaneous hydrolysis of COBE, extended the lifetime of DH/ Cc -PAA bioelectrode, and increased the Faradaic efficiency and the concentration of generated ( R )-ethyl-4-cyano-3-hydroxybutyrate (( R )-CHCN). After 10 h of reaction, the highest concentration of ( R )-CHCN in the biphasic bioelectrocatalytic system was 25.5 mM with 81.2% enantiomeric excess ( ee |
| المشرفين على المادة: | 0 (Nitriles) EC 1.1.1.1 (Alcohol Dehydrogenase) EC 3.- (Hydrolases) EC 3.8.1.- (halohydrin dehalogenase) |
| تواريخ الأحداث: | Date Created: 20200415 Date Completed: 20210413 Latest Revision: 20210413 |
| رمز التحديث: | 20221213 |
| DOI: | 10.1021/jacs.0c01890 |
| PMID: | 32286819 |
| قاعدة البيانات: | MEDLINE |
Find this issue from the American Chemical Society | تدمد: | 1520-5126 |
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| DOI: | 10.1021/jacs.0c01890 |