Direct biocatalytic one-pot-transformation of cyclohexanol with molecular oxygen into ɛ-caprolactone.

The development of a biocatalytic process concept for ɛ-caprolactone, which directly converts cyclohexanol as an easily available industrial raw material into the desired ɛ-caprolactone in a one-pot fashion while only requiring air as sole reagent, is reported. The desired product ɛ-caprolactone was obtained with 94-97% conversion when operating at a substrate concentration in the range of 20-60 mM. At higher substrate concentrations, however, a significant drop of conversion was found. Subsequent detailed studies on the impact of the starting material, intermediate and product components revealed a significant inhibition and partial deactivation of the BVMO by the product ɛ-caprolactone (in particular at higher concentrations) as well as an inhibition of the BVMO by cyclohexanol and cyclohexanone.

[1]  Jessica Rehdorf,et al.  Scale-up of Baeyer–Villiger monooxygenase-catalyzed synthesis of enantiopure compounds , 2010, Applied Microbiology and Biotechnology.

[2]  Michael J. Fink,et al.  Extensive substrate profiling of cyclopentadecanone monooxygenase as Baeyer–Villiger biocatalyst reveals novel regiodivergent oxidations , 2011 .

[3]  W. Thielemans,et al.  Synthesis of polycaprolactone: a review. , 2009, Chemical Society reviews.

[4]  C. Knowles,et al.  Biotransformation of endo-bicyclo[2.2.1 ]heptan-2-ols and endo-bicyclo[3.2.0]hept-2-en-6-ol into the corresponding lactones , 1991 .

[5]  Florian Rudroff,et al.  Efficient Biooxidations Catalyzed by a New Generation of Self‐Sufficient Baeyer–Villiger Monooxygenases , 2009, Chembiochem : a European journal of chemical biology.

[6]  Marko D. Mihovilovic,et al.  Baeyer–Villiger Oxidations , 2012 .

[7]  W. Hummel,et al.  Cloning, expression, and characterization of an (R)-specific alcohol dehydrogenase from Lactobacillus kefir , 2006 .

[8]  U. Bornscheuer,et al.  Discovery, application and protein engineering of Baeyer-Villiger monooxygenases for organic synthesis. , 2012, Organic & biomolecular chemistry.

[9]  Uwe T Bornscheuer,et al.  Exploiting the regioselectivity of Baeyer-Villiger monooxygenases for the formation of beta-amino acids and beta-amino alcohols. , 2010, Angewandte Chemie.

[10]  U. Bornscheuer,et al.  Kinetic resolution of 4-hydroxy-2-ketones catalyzed by a Baeyer-Villiger monooxygenase. , 2006, Angewandte Chemie.

[11]  M. Fraaije,et al.  Recent Developments in the Application of Baeyer–Villiger Monooxygenases as Biocatalysts , 2010, Chembiochem : a European journal of chemical biology.

[12]  J. K.,et al.  Industrial Organic Chemistry , 1938, Nature.

[13]  H. Gröger,et al.  Reduction of Ketones and Aldehydes to Alcohols , 2012 .