Monooxygenases Baeyer-Villiger oxidation

The product (6-hexanolide) is a cyclic ester, or lactone (Section 19.15). Like the Baeyer-Villiger oxidation, an oxygen atom is inserted between the carbonyl group and a carbon attached to it. But peroxy acids are not involved in any way the oxidation of cyclohexanone is catalyzed by an enzyme called cyclohexanone monooxygenase with the aid of certain coenzymes. [Pg.738]

Synthesis of Optically Pure Chiral Lactones by Cyclopentadecanone Monooxygenase-catalyzed Baeyer-Villiger Oxidations... [Pg.344]

Among the most popular oxidative biotransformations, Baeyer-Villiger monooxygenases (BVMOs) belong to the main fields of research. Nowadays, manifold enzymes catalyzing the Baeyer-Villiger oxidation are expressed in common recombinant organisms, such as E. coli or S. cerevisiae. The mechanism of the enzymatic... [Pg.21]

The biocatalytical formation of y-butyrolactones through Baeyer-Villiger oxidation is catalyzed by a number of different monooxygenases, yielding precursors to various natural products [29, 38]. Best enantioselectivities were obtained for the... [Pg.23]

More recently, the formal total syntheses of some bioactive natural products bearing a tetrahydrofurane moiety were achieved by enzymatic Baeyer-Villiger oxidation using cyclopentanone monooxygenases (CPMOs) from Comamonas sp. [Pg.24]

Gagnon R, Grogan G et al (1995) Enzymatic Baeyer-Villiger oxidations of some bicyclo [2.2.1]heptan-2-ones using monooxygenases from Pseudomonas putida NCIMB 10007 enantioselective preparation of a precursor of azadirachtin. J Chem Soc Perkin Trans 1 1505-1511... [Pg.42]

Monooxygenases have been used for the Baeyer-Villiger oxidations to obtain optically active lactones (Figure 32).33 A cyclohexanone monooxygenase from Acinetobacter calcoaceticus has been widely used. In the oxidation of... [Pg.260]

Dynamic kinetic resolution process was also applied to biocatalytic Baeyer-Villiger oxidations. The recombinant E. coli expressing the cyclohexanone monooxygenase from A. calcoaceticus was used for the oxidation of racemic... [Pg.261]

Mihovilovic MD, Rudroff F, Winninger A, Schneider T, Schulz F, Reetz MT (2006) Microbial Baeyer-Villiger oxidation Stereopreference and substrate acceptance of cyclohexanone monooxygenase mutants prepared by directed evolution. Org Lett 8 1221-1224... [Pg.338]

Fig. 4.15 Mechanism of the Baeyer-Villiger oxidation of cyclohexanone using flavin-dependent monooxygenase.

It has been reported that cyclohexanone monooxygenase displays a broad substrate specificity for cyclic ketones38. Moreover, the lactonization of 2-methylcyclohexanone (3), catalyzed by this enzyme, exhibits a regioselectivity comparable with that found for the chemical Baeyer Villiger oxidation oxygen insertion only takes place between the carbonyl group and the substituted carbon center393. [Pg.420]

Flavoprotein monooxygenases mainly use NAD(P)H as electron donor and insert one atom of molecular oxygen into then-substrates. Oxygen activation of flavoprotein monooxygenases involves the (transient) stabilization of a flavin C4a-(hydro) peroxide. This species performs either a nucleophilic or electrophilic attack on the substrate (Fig. 6). Oxygenation reactions catalyzed by flavoprotein monooxygenases include hydroxyla-tions, epoxidations, Baeyer-Villiger oxidations, and sulfoxida-tions (43). [Pg.506]

Oxidations catalyzed by monooxygenases Oxygenations of C-H and C=C bonds forming alcohols, epoxides enantioselective Baeyer-Villiger oxidations of ketones to chiral lactones and of sulfides to chiral sulfoxides nuclear and side-chain hydroxylation of aromatic compounds. [Pg.1104]

Mihovilovic, M. D., Muller, B., Stanetty, P. Monooxygenase-mediated Baeyer-Villiger oxidations. Eur. J. Org. Chem. 2002, 3711-3730. [Pg.541]

Flavin-dependent monooxygenase-mediated Baeyer-Villiger oxidations leading to chiral lactones 02EJO3711. [Pg.169]

Apart from the asymmetric metal catalysis, enantioselective Baeyer-Villiger oxidations mediated by enzymes have been known for some time [32,33,34]. Both whole-cell cultures and isolated enzymes, usually flavin-dependent monooxygenases, can be used to oxidize ketones enantioselectively. For future improvements in the asymmetric Baeyer-VilHger oxidation the use of chiral Lewis acids in combination with an appropriate oxidant seems worthy of intensive investigation. [Pg.768]

Oxidations/hydroxylations of linactivated saturated carbons (polyunsaturated) fatty acids epoxidation and dihydroxylation of alkenes aromatic compounds (- unsaturated diols) hydroxylated compounds and aldehydes diols (and lactonization) enzyme catalyzed Baeyer-Villiger oxidations organic sulfides (sulfoxidation) Be, Mi, Mp, Po, Ra, CytP450 enzymes, monooxygenases SLO An, Nc, Po Pp (mutant strain), Ce Go, Ps Bp, Go, Ko, Ps, HLADH Ac, Ps, CHO BY, An, Ceq, Mi, Po, CPO, BSA... [Pg.179]

Enzymatic Baeyer-Villiger Oxidations by Flavin Dependent Monooxygenases" Walsh. C.T. Chen, Y.-C.J. Angew. Chem. Int Ed., Engl, 1988, 27, 333. [Pg.185]