Hydrogenation biocatalytic reductions

Formate is one of the most representative hydrogen sources for the biocatalytic reduction because CO2 formed by the oxidation of formate is released easily from the reaction system [4]. For example, for the reduction of aromatic ketones by the... 

Prochiral aryl and dialkyl ketones are enantioselectively reduced to the corresponding alcohols using whole-cell bioconversions, or an Ir1 amino sulfide catalyst prepared in situ.695 Comparative studies show that the biocatalytic approach is the more suitable for enantioselective reduction of chloro-substituted ketones, whereas reduction of a,/ -unsaturated compounds is better achieved using the Ir1 catalyst. An important step in the total synthesis of brevetoxin B involves hydrogenation of an ester using [Ir(cod)(py) P(cy)3 ]PF6.696... 

Another very recent development in the field of enzymatic domino reactions is a biocatalytic hydrogen-transfer reduction of halo ketones into enantiopure epoxides, which has been developed by Faber, Bornscheuer and Kroutil. Interestingly, the reaction was carried out with whole lyophilized microbial cells at pH ca. 13. Investigations using isolated enzymes were not successful, as they lost their activity under these conditions [26]. 

Poessl, T.M., Kosjek, B., Ellmer, U. et al. (2005) Non-racemic halohydrins via biocatalytic hydrogen-transfer reduction of halo-ketones and one-pot cascade reaction to enantiopure epoxides. Advanced Synthesis and Catalysis, 347 (14), 1827-1834. 

Edegger, K., Stampfer, W., Seisser, B. et al. (2006) Regio- and stereoselective reduction of diketones and oxidation of diols by biocatalytic hydrogen transfer. European Journal of Organic Chemistry, (8), 1904—1909. 

We focus here on the use of oxygenases, particularly the blue copper oxygenases, such as laccase and bilirubin oxidase, which can biocatalytically reduce oxygen directly to water at relatively high reduction potentials under mild conditions. First, however, we will briefly consider reports on the use of hydrogen peroxide as an oxidant in biocatalytic fuel cells. 

The use of hydrogen peroxide as an oxidant is not compatible with the operation of a biocatalytic fuel cell in vivo, because of low levels of peroxide available, and the toxicity associated with this reactive oxygen species. In addition peroxide reduction cannot be used in a membraneless system as it could well be oxidized at the anode. Nevertheless, some elegant approaches to biocatalytic fuel cell electrode configuration have been demonstrated using peroxidases as the biocatalyst and will be briefly reviewed here. 

Most catalysts originally developed for C=C bonds show a rather poor performance for the hydrogenation of many ketones. However, this situation changed dramatically when it was found that selected Ru-binap and later Ru-binap-dia-mine complexes achieve excellent enantioselectivities, as well as very high TONs and TOFs, for a variety of ketones [92]. Since then, it has been demonstrated that many a- and yS-functionalized, as well as aromatic ketones, are suitable substrates for hydrogenation with industrially viable catalytic results. For the reduction of various ketones biocatalytic methods are an industrially viable alternative to chemocatalysts [15]. 

The yields and ee values were significantly higher in the biocatalytic processes, whereas the nonenzymatic reductions needed substantially lower amounts of substrates (cofactor, buffer, cosubstrate) because only hydrogen was used as a... 

Non-standard equipment was necessary for all enantioselective reductions for the hydrogenations, a high pressure reactor, for the biocatalytic processes sophisticated continuous reaction systems with various feedback loops. 

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