Abstract
Electroenzymatic syntheses combine oxidoreductase‐catalysed reactions with electrochemical reactant supply. The use of ionic liquids as performance additives can contribute to overcoming existing limitations of these syntheses. Here, we report on the influence of different water‐miscible ionic liquids on critical parameters such as conductivity, biocatalyst activity and stability or substrate solubility for three typical electroenzymatic syntheses. In these investigations promising ionic liquids were identified and have been used as additives for batch electrolyses on preparative scale for the three electroenzymatic systems. It was possible to improve the space‐time‐yield for the electrochemical regeneration of NADPH by a factor of three. For an amino acid oxidase catalysed resolution of a methionine racemate with ferrocene‐mediated electrochemical regeneration of the enzyme‐bound cofactor FAD a 50 % increase in space time yield and 140 % increase in catalyst utilisation (TTN) were achieved. Furthermore, for the chloroperoxidase‐catalysed synthesis of (R)‐phenylmethylsulfoxide with electrochemical generation of the required cosubstrate H~2~O~2~ the space time yield and the catalyst utilisation were improved by a factor of up to 4.2 depending on the ionic liquids used.