Reaction: cyclohexanone + NADPH + H+ + O2 = hexano-6-lactone + NADP+ + H2O
For diagram of reaction click here.
Other name(s): cyclohexanone 1,2-monooxygenase; cyclohexanone oxygenase; cyclohexanone:NADPH:oxygen oxidoreductase (6-hydroxylating, 1,2-lactonizing)
Systematic name: cyclohexanone,NADPH:oxygen oxidoreductase (lactone-forming)
Comments: A flavoprotein (FAD). In the catalytic mechanism of this enzyme, the nucleophilic species that attacks the carbonyl group is a peroxyflavin intermediate that is generated by reaction of the enzyme-bound flavin cofactor with NAD(P)H and oxygen [2]. This enzyme is able to catalyse a wide range of oxidative reactions, including enantioselective Baeyer-Villiger reactions [3], sulfoxidations [4], amine oxidations [5] and epoxidations [6].
Links to other databases: BRENDA, EAWAG-BBD, EXPASY, KEGG, Metacyc, PDB, CAS registry number: 52037-90-8
References:
1. Donoghue, N.A., Morris, D.B. and Trudgill, P.W. The purification and properties of cyclohexanone oxygenase from Nocardia globerula CL1 and Acinetobacter NCIB 9871. Eur. J. Biochem. 63 (1976) 175-192. [PMID: 1261545]
2. Sheng, D., Ballou, D.P. and Massey, V. Mechanistic studies of cyclohexanone monooxygenase: chemical properties of intermediates involved in catalysis. Biochemistry 40 (2001) 11156-11167. [PMID: 11551214]
3. Stewart, J.D. Cyclohexanone monooxygenase: a useful reagent for asymmetric Baeyer-Villiger reactions. Curr. Org. Chem. 2 (1998) 195-216.
4. Chen, G., Kayser, M.M., Milhovilovic, M.D., Mrstik, M.E., Martinez, C.A. and Stewart, J.D. Asymmetric oxidations at sulfur catalyzed by engineered strains that overexpress cyclohexanone monooxygenase. New J. Chem. 23 (1999) 827-832.
5. Ottolina, G., Bianchi, S., Belloni, B., Carrea, G. and Danieli, B. First asymmetric oxidation of tertiary amines by cyclohexanone monooxygenase. Tetrahedron Lett. 40 (1999) 8483-8486.
6. Colonna, S., Gaggero, N., Carrea, G., Ottolina, G., Pasta, P. and Zambianchi, F. First asymmetric epoxidation catalysed by cyclohexanone monooxygenase. Tetrahedron Lett. 43 (2002) 1797-1799. [PMID: ]