Multienzymatic Processes Involving Baeyer-Villiger Monooxygenases

Baeyer-Villiger monooxygenases (BVMOs) are flavin-dependent oxidative enzymes capable of catalyzing the insertion of an oxygen atom between a carbonylic Csp(2) and the Csp(3) 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 alpha,beta-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.

Automated summary

Baeyer-Villiger monooxygenases (BVMOs) are flavin-dependent oxidative enzymes that catalyze the transformation of linear and cyclic ketones into esters and lactones by inserting an oxygen atom between a carbonylic Csp(2) and the Csp(3) at the alpha position. BVMOs can be included in cascade reactions with other redox enzymes, such as alcohol dehydrogenases or ene-reductases, to achieve the direct conversion of alcohols or alpha,beta-unsaturated carbonylic compounds into the corresponding esters. Employing multienzymatic strategies with BVMOs using whole cells or isolated enzymes in sequential or parallel methods can highlight the advantages and recent advances for overcoming drawbacks when using BVMOs in these techniques.