Recent Developments in the Application of Baeyer–Villiger Monooxygenases as Biocatalysts

Abstract

Baeyer–Villiger monooxygenases (BVMOs) represent a specific class of monooxygenases that are capable of catalyzing a variety of oxidation reactions, including Baeyer–Villiger oxidations. The recently elucidated BVMO crystal structures have provided a more detailed insight into the complex mechanism of these flavin‐containing enzymes. Biocatalytic studies on a number of newly discovered BVMOs have shown that they are very potent oxidative biocatalysts. In addition to catalyzing the regio‐ and enantioselective Baeyer–Villiger oxidations of a wide range of carbonylic compounds, epoxidations, and enantioselective sulfoxidations have also been shown to be part of their catalytic repertoire. This review provides an overview on the recent developments in BVMO‐mediated biocatalytic processes, identification of the catalytic role of these enzymes in metabolic routes and prodrug activation, as well as the efforts in developing effective biocatalytic methodologies to apply BVMOs for the synthesis of high added value compounds.

Functional assembly of camphor converting two-component Baeyer–Villiger monooxygenases with a flavin reductase from E. coli

“…Predominantly, enzymes that function as a single polypeptide (designated as Type I BVMOs: Willetts 1997) have been mostly investigated and are applied as biocatalysts in organic synthesis (de Gonzalo et al 2010). Nowadays, a variety of Type I BVMOs are available and the historical prototype cyclohexanone monooxygenase (CHMO) from Acinetobacter calcoaceticus NCIMB 9871, which was discovered and first purified almost 40 years ago (Donoghue et al 1976), has been outranged by other candidates such as cyclododecanone monooxygenase (CDMO) from Rhodococcus ruber SC1 and CHMO from Xantobacter sp.…”

Snapshots of Enzymatic Baeyer-Villiger Catalysis

“…BVMOs are promising targets for biocatalytic applications in synthetic and pharmaceutical chemistry (11,12). Phenylacetone monooxygenase (PAMO, EC 1.14.13.92) from Thermobifida fusca features several attractive properties: it is thermostable, tolerant to organic solvents (13,14), and catalyzes enantioselective Baeyer-Villiger oxidations and sulfoxidations on a number of substrates in addition to phenylacetone (15).…”

Utilization of Volatile Organic Compounds as an Alternative for Destructive Abatement

“…In the case of longer chain alkanes, the oxidation starts usually in the terminal methyl group to give the primary alcohol, which is further oxidized to the corresponding aldehyde, and finally converted into fatty acid [210,213]. The alkane-activating enzymes are the mono-oxygenases, which are widely used as biocatalysts in several processes [214][215][216]. Temperature is an important factor in these processes, since it affects the solubility of the alkanes and the stability of the enzymes.…”