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Open AccessArticle

Lipase-Catalyzed Chemoselective Ester Hydrolysis of Biomimetically Coupled Aryls for the Synthesis of Unsymmetric Biphenyl Esters

1
Institute for Biophysical Chemistry, Hannover Medical School, 30625 Hannover, Germany
2
Centre of Biomolecular Drug Research (BMWZ), Leibniz University Hannover, 30167 Hannover, Germany
*
Author to whom correspondence should be addressed.
Academic Editor: Marco Filice
Molecules 2019, 24(23), 4272; https://doi.org/10.3390/molecules24234272
Received: 30 October 2019 / Revised: 17 November 2019 / Accepted: 21 November 2019 / Published: 23 November 2019
(This article belongs to the Special Issue Lipases and Lipases Modification 2019)
Lipases are among the most frequently used biocatalysts in organic synthesis, allowing numerous environmentally friendly and inexpensive chemical transformations. Here, we present a biomimetic strategy based on iron(III)-catalyzed oxidative coupling and selective ester monohydrolysis using lipases for the synthesis of unsymmetric biphenyl-based esters under mild conditions. The diverse class of biphenyl esters is of pharmaceutical and technical relevance. We explored the potency of a series of nine different lipases of bacterial, fungal, and mammalian origin on their catalytic activities to cleave biphenyl esters, and optimized the reaction conditions, in terms of reaction time, temperature, pH, organic solvent, and water–organic solvent ratios, to improve the chemoselectivity, and hence control the ratio of unsymmetric versus symmetric products. Elevated temperature and increased DMSO content led to an almost exclusive monohydrolysis by the four lipases Candida rugosa lipase (CRL), Mucor miehei lipase (MML), Rhizopus niveus lipase (RNL), and Pseudomonas fluorescens lipase (PFL). The study was complemented by in silico binding predictions to rationalize the observed differences in efficacies of the lipases to convert biphenyl esters. The optimized reaction conditions were transferred to the preparative scale with high yields, underlining the potential of the presented biomimetic approach as an alternative strategy to the commonly used transition metal-based strategies for the synthesis of diverse biphenyl esters. View Full-Text
Keywords: lipases; biphenyl esters; biocatalysis; chemoselectivity; biomimetic synthesis; organic synthesis lipases; biphenyl esters; biocatalysis; chemoselectivity; biomimetic synthesis; organic synthesis
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Ehlert, J.; Kronemann, J.; Zumbrägel, N.; Preller, M. Lipase-Catalyzed Chemoselective Ester Hydrolysis of Biomimetically Coupled Aryls for the Synthesis of Unsymmetric Biphenyl Esters. Molecules 2019, 24, 4272.

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