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The overcoming of thermodynamic limitations in the synthesis of optically active ketone cyanohydrins by using organic solvent‐free systems has been investigated. Therefore, substrates with known unfavorable results within hydroxynitrile lyase‐catalyzed reactions were selected for the determination of limitations and bottlenecks in ketone cyanohydrin synthesis. The highly ( S )‐selective hydroxynitrile lyase from Manihot esculenta ( Me HNL) has been chosen for the conversion of acetophenone and the corresponding derivatives, which are substrates that exhibit only low grades of conversion also with several other hydroxynitrile lyases. With organic solvent‐free systems under optimized reaction conditions conversions up to 78 % with>99.0 ee ( S ) were obtained. Finally, 5 mL of ( S )‐acetophenone cyanohydrin with an enantiomeric excess of 98.5 % ee ( S ) were synthesized.
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Langermann et al. (2007) studied this question.
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