Reductive biotransformation of diethyl β-, γ- and δ-oxoalkylphosphonates by cells of baker’s yeast (original) (raw)
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Phosphorus, Sulfur, and Silicon and the Related Elements, 2017
The conversion path and the complex procedure of products separation elaborated for ketophosphonates and hydroxyphosphonates formed during the biotransformations of aminophoshonates are reported. Penicillium funiculosum (Thom 3), Geotrichum candidum (6593), Beauveria bassiana (271B) were applied for bioconversion of a racemic mixture of the phosphonic analogue of isoleucine (Ile P), whereas P. funiculosum (Thom 3), F. oxysporum (DSM 12646) and Trigonopsis variabilis (DSM 70714) were used for transformation of the phosphonic analogue of valine (Val P). The biocatalytic processes were analysed to confirm and to compare the path and the selectivity of the biological conversion of aminophosphonates with one (Val P) and two stereogenic centers (Ile P). The efforts undertaken allowed to demonstrate, that applied biocatalysts act in two steps. A racemic mixture of substrates was bioconverted via oxidative deamination with formation of ketones, which were subsequently bioreduced in the next step of the process. As it was proved the selectivity of the bioreactions differs depending on the structure of the substrate. The first step of the process in the case of the phosphonic analogue of valine 4 allowed to obtain the pure unreacted enantiomer of aminophosphonate (R) whereas the biotransformation of Ile P was unselective. Both ketone intermediates were reduced in a non-selective way. The results were evaluated by NMR, MS and IR techniques, which confirmed the path of the biocatalytic two steps redox reaction: oxidation and reduction.
2016
Three strains of microorganisms: Bacillus subtilis, Serratia liquefaciens and Escherichia coli were tested as whole-cell biocatalysts for the kinetic resolution of isomers of two new phosphonoacetic acid derivatives. Used compounds possess two chiral centres-one at the carbon adjacent to both functional groups and the other at the phosphorus. Biocatalytic hydrolysis of 2-butyryloxy-2-(butoxyetoxyphosphinyl)acetic acid and 2-butyryloxy-2-(isobutoxyetoxyphosphinyl)acetic acid with whole cells of Bacillus subtilis produced corresponding hydroxyphosphonates with diastereoselectivity ranging from 50 to 60%.
Biocatalytic syntheses of chiral non-racemic 2-hydroxyalkanephosphonates
Tetrahedron: Asymmetry, 2001
A series of 2-oxoalkanephosphonates 2 were screened for reduction with Geotrichum candidum. Only diethyl 2-oxopropanephosphonate 2a underwent asymmetric reduction to give (+)-(R)-diethyl 2-hydroxypropanephosphonate 3a with 98% e.e. In turn, a series of racemic 2-hydroxyalkanephosphonates 3 were acetylated under kinetic resolution conditions in the presence of various lipases to give the corresponding 2-acetoxyalkanephosphonates 4 and recovered alcohols 3 in good yields and with e.e. up to 93%.
Phosphonates enantiomers receiving with fungal enzymatic systems
Microbial Cell Factories
Background Phosphonates derivatives are in the area of interests because of their unique chemical-physical features. These compounds manifest variety of biological interactions within the sensitive living cells, including impact on particular enzymes activities. Biological “cause and effect” interactions are based upon the specific matching between the structures and/or compounds and this is usually the result of proper optical configurations of particular chiral moieties. Presented research is targeted to the phosphonates with the heteroatom incorporated in their side functionalities. Such molecules are described as possible substrates of bioconversion for the first time lately and this field is not fully explored. Results Presented research is targeted to the synthesis of pure hetero-phosphonates enantiomers. The catalytic activity of yeasts and moulds were tested towards two substrates: the thienyl and imidazole phosphonates to resolve their racemic mixtures. Biotransformations c...
Tetrahedron, 2001
AbstractÐCyclic dialkyl (3-oxo-1-cycloalkenyl) phosphonates were subjected to baker's yeast-mediated enantioselective reductions to afford the corresponding dialkyl (3-hydroxy-1-alkenyl) phosphonates. The six-and seven-membered ring enones were reduced with moderate to good enantiomeric excesses, whereas the ®ve-membered ring substrate always yielded the double bond reduced compound. The use of different reduction conditions did not improve the ee's markedly, but it was found, for the six-membered analogues, that the alkyl groups held by phosphorus in¯uence dramatically the enantioselectivity of the reduction, leading to up to 95% enantiomeric excess. q ² The structure of 5 was unambiguously attributed by comparison with an authentic sample. 12
Application of cyanobacteria as biocatalysts for the reduction of diethyl 2-oxopropylphosphonate
Chemik Science-Technique-Market
The aim of the study was applying of autotrophic microorganisms as a biocatalyst in the reduction of oxoalkylphosphonates. Cyanobacteria strains Arthrospira maxima CCALA 027 and Nodularia sphaerocarpa CCALA 114 are capable to reduce diethyl 2- oxopropylphosphonate to the corresponding diethyl 2- hydroxypropylphosphonate. The degree of conversion of the substrate was respectively 26.4% and 12.9%, and the optical purity of the product in both cases was over 99%.