title: Enantio convergent biotransformation of O,O-dimethyl-4-oxoazetidin-2-ylphosphonate using fungal cells of Penicillium minioluteum and purified enzymes.
abstract: This report presents the bioconversion of O,O-dimethyl-4-oxoazetidin-2-ylphosphonate 1 performed in two ways: with the enzymatic system of P. minioluteum and with the application of purified enzymes: penicillinase and two proteases of different origin. Recorded NMR spectra allowed confirming the reaction progress and also postulating possible mechanism of conversion. The path of bioconversion was defined as enantio convergent process for both modes of applied biocatalysts. This means that kinetically driven resolution of racemic mixture of the substrate leads to the one enantiomer of the product. The bioconversion started from ester bond hydrolysis (equally in both enantiomers) with the conversion degree from 30% (whole-cell) to 35% (isolated enzymes) and with the production of optically pure monoester (compound 2; 100% of e.e). For whole-cell bioprocess it was the initiative step for the enantioselective amide bond hydrolysis, what resulted in synthesis of desired product 3-amino-3-phosphonopropanoic acid 4. However, the most effective enzymatic hydrolysis of ester bond performed with penicillinase from Enterobacter cloacae led only to the monoester product 2.
authors.affiliation: Department of Bioorganic Chemistry, Faculty of Chemistry, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland. Electronic address: natalia.kmiecik@pwr.edu.pl.
authors.forename: Natalia
authors.initials: N
authors.lastname: Kmiecik
authors.affiliation: Department of Bioorganic Chemistry, Faculty of Chemistry, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland.
authors.forename: Ewa
authors.initials: E
authors.lastname: Żymańczyk-Duda
mesh_terms: D000069976:Bacillus licheniformis / Q000201:enzymology*; D001711:Biotransformation; D016972:Enterobacter cloacae / Q000201:enzymology*; D006868:Hydrolysis; D007700:Kinetics; D063065:Organophosphonates / Q000378:metabolism*; D010405:Penicillinase / Q000378:metabolism; D010407:Penicillium / Q000166:cytology / Q000201:enzymology / Q000378:metabolism*; D010447:Peptide Hydrolases / Q000378:metabolism; D012233:Rhizopus / Q000201:enzymology*; D013237:Stereoisomerism
chemical_list: D063065:Organophosphonates; D010447:Peptide Hydrolases; D010405:Penicillinase
keywords: Biotransformation; Fungus; Hydrolases; Phosphonates