Journal of Biotechnology, Computational Biology and Bionanotechnology RESEARCH PAPER Microbial biotransformation of two phosphonoacetic acid derivatives (original) (raw)

Enzymes in Organic Chemistry, 11:[1] Hydrolase-Catalyzed Resolution ofα- andβ-Hydroxyphosphonates and Synthesis of Chiral, Non-Racemicβ-Aminophosphonic Acids

Advanced Synthesis & Catalysis, 2003

The enantioselective acylation of racemic diisopropyl aand b-hydroxyphosphonates by hydrolases in t-butyl methyl ether with isopropenyl acetate as acyl donor is limited by the narrow substrate specificity of the enzymes. High enantiomeric excesses (up to 99%) were obtained for the acetates of (S)diisopropyl 1-hydroxy-(2-thienyl)methyl-, 1-hydroxyethyl-and 1-hydroxyhexylphosphonate and (R)-diisopropyl 2-hydroxypropylphosphonate. The hydrolysis of a variety of b-chloroacetoxyphosphonates by the lipase from Candida cylindracea and protease subtilisin in a biphasic system gives (S)-b-hydroxyphosphonates (ee 51 ± 92%) enantioselectively. (S)-2-Phenyl-2-hydroxyethyl-and (S)-3-methyl-2-hydroxybutylphosphonates (ee 96% and 99%, respectively) were transformed into (R)-2-aminophosphonic acids of the same ee.

The Hydrolysis of Phosphinates and Phosphonates: A Review

Molecules

Phosphinic and phosphonic acids are useful intermediates and biologically active compounds which may be prepared from their esters, phosphinates and phosphonates, respectively, by hydrolysis or dealkylation. The hydrolysis may take place both under acidic and basic conditions, but the C-O bond may also be cleaved by trimethylsilyl halides. The hydrolysis of P-esters is a challenging task because, in most cases, the optimized reaction conditions have not yet been explored. Despite the importance of the hydrolysis of P-esters, this field has not yet been fully surveyed. In order to fill this gap, examples of acidic and alkaline hydrolysis, as well as the dealkylation of phosphinates and phosphonates, are summarized in this review.

Reductive biotransformation of diethyl β-, γ- and δ-oxoalkylphosphonates by cells of baker’s yeast

Enzyme and Microbial Technology, 2000

Enantiomerically pure hydroxyalkylphosphonates (over 95% of enantiomeric excess) were obtained by asymmetric reductive biotransformation of a variety of oxoalkylphosphonates catalyzed by baker's yeast. In the most cases the biotransformations were carried out in water under aerobic conditions using whole cell system. In the case of compounds unreactive under these conditions the anaerobic reduction was applied.

Stereochemical aspects of the asymmetric synthesis of chiral α,β-dihydroxy phosphonates. Synthesis of α,β-dihydroxy phosphonic acids

Tetrahedron: Asymmetry, 1996

Steret~ontrol in the asymmetric phosphonylation of aldehydes via organophosphorous esters has bccn obtained starting from chiral aldehydes. The nature of the O-protecting group is crucial to obtain, in terms of diastereoseleetivity and chemical yields, the best results. An ab/n/t/o molecular orbital study on 2-silyioxy propanal and MM2 studies on 2-alkoxy propanai show the existence of stable cyclic and acyclic conformers, which are presumably responsible for the high syn diastereoseleetivity observed in the addition of non-metal carrying phosphites.

Biotransformations of 2-hydroxy-2-(ethoxyphenylphosphinyl)acetic acid and the determination of the absolute configuration of all isomers

Bioorganic Chemistry, 2015

2-Hydroxy-2-(ethoxyphenylphosphinyl)acetic acid, a new type of organophosphorus compound possessing two stereogenic centers, was investigated. Racemic 2-butyryloxy-2-(ethoxyphenylphosphinyl)acetic acid was synthesized and hydrolyzed using four bacterial species as biocatalysts. In all cases the reaction was more or less stereoselective and isomers bearing a phosphorus atom with an (S P)-configuration were hydrolyzed preferentially. The observed 1 H and 31 P NMR chemical shifts of Mosher esters of 2-hydro xy-2-(ethoxyphenylphosphinyl)acetic acid were correlated with the configurations of both stereogenic centers of all four stereoisomers.

Synthesis of phosphonates from phenylphosphonic acid and its monoesters

Synthetic Communications, 2019

Possibilities for the mono-and diesterification of phenylphosphonic acid were evaluated considering the microwave(MW)-assisted direct esterification, and the alkylating esterification. It was found that regarding the monoesterification, the reaction with 15-fold alcohol excess in the presence of [bmim][BF 4 ] additive utilizing MWs is superior than the approach by alkylation. At the same time, for the conversion of the monoester intermediate to the diester, the reaction with alkyl halides in the presence of triethylamine as the base, again under MW irradiation, was found to be the method of choice. Phosphonates with both identical and different alkoxy groups were made available.