Lipase-Catalyzed Kinetic Resolution of Dimethyl and Dibutyl 1-Butyryloxy-1-carboxymethylphosphonates

• Published in: Catalysts
• Main Author: Paulina Majewska
• Format: Article in Journal/Newspaper
• Language: English
• Published: MDPI AG 2021
• Subjects: biocatalysis; hydroxyphosphonates; lipolytic activity; determination of absolute configuration; enantiomers; Chemical technology; TP1-1185; Chemistry; QD1-999; Rugosa; Antarc*; Antarctica
• Online Access: https://doi.org/10.3390/catal11080956; https://doaj.org/article/8720d5598912469a98a31e9d65e47332

The main objective of this study is the enantioselective synthesis of carboxyhydroxyphosphonates by lipase-catalyzed reactions. For this purpose, racemic dimethyl and dibutyl 1-butyryloxy-1-carboxymethylphosphonates were synthesized and hydrolyzed, using a wide spectrum of commercially available lipases from different sources (e.g., fungi and bacteria). The best hydrolysis results of dimethyl 1-butyryloxy-1-carboxymethylphosphonate were obtained with the use of lipases from Candida rugosa , Candida antarctica , and Aspergillus niger , leading to optically active dimethyl 1-carboxy-1-hydroxymethylphosphonate (58%–98% enantiomeric excess) with high enantiomeric ratio (reaching up to 126). However, in the case of hydrolysis of dibutyl 1-butyryloxy-1-carboxymethylphosphonate, the best results were obtained by lipases from Burkholderia cepacia and Termomyces lanuginosus , leading to optically active dibutyl 1-carboxy-1-hydroxymethylphosphonate (66%–68% enantiomeric excess) with moderate enantiomeric ratio (reaching up to 8.6). The absolute configuration of the products after biotransformation was also determined. In most cases, lipases hydrolyzed ( R ) enantiomers of both compounds.