Asymmetric Amination of Secondary Alcohols by using a Redox-Neutral Two-Enzyme Cascade

Abstract Multienzyme cascade approaches for the synthesis of optically pure molecules from simple achiral compounds are desired. Herein, a cofactor self‐sufficient cascade protocol for the asymmetric amination of racemic secondary alcohols to the corresponding chiral amines was successfully constructed by employing an alcohol dehydrogenase and a newly developed amine dehydrogenase. The compatibility and the identical cofactor dependence of the two enzymes led to an ingenious in situ cofactor recycling system in the one‐pot synthesis. The artificial redox‐neutral cascade process allowed the transformation of racemic secondary alcohols into enantiopure amines with considerable conversions (up to 94 %) and >99 % enantiomeric excess at the expense of only ammonia; this method thus represents a concise and efficient route for the asymmetric synthesis of chiral amines.