Multienzymatic Processes Involving Baeyer–Villiger Monooxygenases

Gonzalo De Gonzalo,Andrés R Alcántara

doi:10.3390/catal11050605

Gonzalo De Gonzalo, Andrés R Alcántara

Open Access

https://doi.org/10.3390/catal11050605

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Abstract

Baeyer–Villiger monooxygenases (BVMOs) are flavin-dependent oxidative enzymes capable of catalyzing the insertion of an oxygen atom between a carbonylic Csp2 and the Csp3 at the alpha position, therefore transforming linear and cyclic ketones into esters and lactones. These enzymes are dependent on nicotinamides (NAD(P)H) for the flavin reduction and subsequent reaction with molecular oxygen. BVMOs can be included in cascade reactions, coupled to other redox enzymes, such as alcohol dehydrogenases (ADHs) or ene-reductases (EREDs), so that the direct conversion of alcohols or α,β-unsaturated carbonylic compounds to the corresponding esters can be achieved. In the present review, the different synthetic methodologies that have been performed by employing multienzymatic strategies with BVMOs combining whole cells or isolated enzymes, through sequential or parallel methods, are described, with the aim of highlighting the advantages of performing multienzymatic systems, and show the recent advances for overcoming the drawbacks of using BVMOs in these techniques.

Highlights

The elucidation and rational understanding of the internal organization of the different biocatalytic reactions occurring inside biological cells, in which several enzymatic reactions proceed in a concatenated manner, is one of the basis of Systems Biology [1]
Inside this type of enzymes, Baeyer–Villiger monooxygenases (BVMOs) are undoubtedly one of the most attractive members of this family; these flavin-dependent oxidative enzymes [16,17,18,19,20] are capable of catalyzing the insertion of an oxygen atom between a carbonylic Csp2 and the Csp3 at the alpha position, transforming linear and cyclic ketones into esters and lactones [20,21,22,23,24,25,26,27], as schematized in Scheme 1
The production of ECL starting from cyclohexanol employing E. coli cells of alcohol dehydrogenases (ADHs) and AcCHMO has been studied by using a computational approach in 2017 [55], applying a kinetic model for the study this cascade reaction in both batch and fed-batch synthesis

Summary

Introduction

The elucidation and rational understanding of the internal organization of the different biocatalytic reactions occurring inside biological cells, in which several enzymatic reactions proceed in a concatenated manner, is one of the basis of Systems Biology [1]. Multi-Step Reactions Including BVMO Activity Catalyzed by Whole Cells

Results

Conclusion