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Abstract Electrochemical regeneration of nicotinamide cofactors has been discussed as a promising, clean, and sustainable technology since the 1980s. However, most concepts for the coupling of this technology to enzymes suffer from low productivities, insufficient stabilities, or are difficult to scale up. We have developed an electrochemical cell for the efficient regeneration of NAD(P)H, which can be coupled to a reduction reaction catalyzed by the thermophilic alcohol dehydrogenase from Thermus sp. Octane, as second organic phase avoided product inhibition and allowed for the production of (1 S ,3 S )‐3‐methylcyclohexanol at a diastereomeric excess of 96 % from the corresponding racemic ketone with a productivity of 0.13 g L −1 h −1 and a current efficiency of 85 %. After 10 h, the experiment was actively terminated and the final product concentration reached was 1.32 g L −1 . In our opinion this concept defines a new state of the art in electroenzymology and provides a strong basis for applications in organic synthesis.
Höllrigl et al. (Mon,) studied this question.