A flower-like nanobioreactor was prepared for resolution of ibuprofen in organic solvents. Ultrasound irradiation has been used to improve the enzyme performance of APE1547 (a thermophilic esterase from the archaeon Aeropyrum pernix K1) in the enantioselective esterification. Under optimum reaction conditions (ultrasound power, 225 W; temperature, 45 °C; water activity, 0.21), the immobilized APE1547 showed an excellent catalytic performance (enzyme activity, 13.26 μmol/h/mg; E value, 147.1). After ten repeated reaction batches, the nanobioreactor retained almost 100% of its initial enzyme activity and enantioselectivity. These results indicated that the combination of the immobilization method and ultrasound irradiation can enhance the enzyme performance dramatically.
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http://dx.doi.org/10.3390/molecules21050565 | DOI Listing |
J Org Chem
December 2024
Institute and State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, P. R. China.
An asymmetric tandem esterification/Michael addition reaction of β-keto acylpyrazoles with -hydroxychalcones has been established under the catalysis of a bifunctional squaramide-tertiary amine. A wide variety of biorelevant 3,4-dihydrocoumarin derivatives were generally obtained in high yields (up to 93%) with excellent diastereo- and enantioselectivities (>19:1 dr, up to 93% ee) under mild reaction conditions. This reaction represents the successful application of β-keto acylpyrazoles as 2C building blocks in catalytic asymmetric cyclizations.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain.
Angew Chem Int Ed Engl
November 2024
Laboratory of Biocatalysis and Biotransformation, Department of Drugs Technology and Biotechnology, Faculty of Chemistry, Warsaw University of Technology, Koszykowa 75, 00-662, Warsaw, Poland.
Dynamic kinetic resolution (DKR) is a key method used to prepare optically pure compounds in 100 % theoretical yield starting from racemic substrates by combining the interconversion of substrate enantiomers with an enantioselective transformation. Various chemoenzymatic DKR approaches have been developed to deracemize secondary alcohols, typically requiring an organic solvent to facilitate enantioselective acylation, primarily catalyzed by lipases, alongside racemization mediated by an achiral, non-enzymatic catalyst. Achieving both steps in an aqueous solution remained elusive.
View Article and Find Full Text PDFAcc Chem Res
December 2024
Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China.
Chemistry
November 2024
Dipartimento di Chimica e Biologia "A. Zambelli", Università di Salerno, Via Giovanni Paolo II, 84081, Fisciano, Italy.
Optically active mandelic acid esters represent a highly valuable class of building blocks in organic synthesis and recurrent motifs embedded in bioactive compounds and drugs. Herein, we provide an enantioselective one-pot synthesis based on Knoevenagel condensation/asymmetric epoxidation/domino ring-opening hydrolysis (DROH) sequence to the crude mandelic acids, which underwent a final esterification step to (R)-methyl mandelates. These products have been obtained in good to high overall yield and enantioselectivity, using commercially and widely available reagents and catalyst including aldehydes, phenylsulfonyl acetonitrile, cumyl hydroperoxide, water and an epi-quinine-derived urea as the organocatalyst.
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