Biocatalysis asymmetric oxidation

Matsuda T, Yamanaka R et al (2009) Recent progress in biocatalysis for asymmetric oxidation and reduction. Tetrahedron Asymmetry 20 513-557... 

When comparing chemical and biocatalytic methods, one could say that, especially for asymmetric oxidations, enzymatic methods enter the scene. This is most evident in the area of asymmetric Baeyer-Villiger oxidation, where biocatalysts take the lead and homogeneous chiral catalysts lag far behind in terms of ee values. Significant progress can be expected in the area of biocatalysis due to the advancement in enzyme production technologies and the possibility of tailor-made enzymes. 

Alphand, V., Furstoss, R. Asymmetric Baeyer-Villiger oxidation using biocatalysis. Asymmetric Oxidation Reactions). 2001,214-227... 

It also has to be stressed that many useful redox enzymes for asymmetric oxidations are not commercially available as isolated enzymes—alcohol dehydrogenases are the main exception here— but have to be isolated from the wild-type organism or produced in recombinant form. For that reason, applied biocatalysis is a multidisciplinary field where the expertise of biologists, chemists, and engineers is required. 

The oxidation of heteroatoms and, in particular, the conversion of sulfides to asymmetric sulfoxides has continued to be a highly active field in biocatalysis. In particular, the diverse biotransformations at sulfur have received the majority of attention in the area of enzyme-mediated heteroatom oxidation. This is particularly due to the versatile applicability of sulfoxides as chiral auxiliaries in a variety of transformations coupled with facile protocols for the ultimate removal [187]. 

The large-scale resolution of racemic 2-alkanols to enantiomerically pure (R-)-and (S-t-)-alkanols by lipase shows environmental, health and safety advantages of biocatalysis compared with nonenzymatic syntheses. The biocatalytic Baeyer-Villi-ger oxidation of racemic bicyclo[3.2.0]-hept-2-en-6-one to enantiomerically pure 2-oxabicyclo[3.3.0]-oct-6-en-3-one and 3-oxabicyclo[3.3.0]-oct-6-en-2-one by CHMO represents an asymmetric Baeyer-Villiger oxidation. 

With the access to diverse and stable biocatalysts, more and more conventional chemical processes (first generation) in pharmaceutical manufacturing have been replaced by second-generation biocatalysis processes with substantial impact on the pharmaceutical industry. In this chapter, some commonly used biocatalytic reactions for chiral preparation, including hydrolytic reactions, acyl and glycosyl transfer reactions, asymmetric reduction/ oxidation reactions, and asymmetric formation of C-C bonds, are introduced and exemplified by the research achievements developed by the authors laboratory as well as other research groups. Some of the bioprocesses described herein have been successfully applied on pilot or even industrial scale. ... 

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