Recombinant Cyanobacteria for the Asymmetric Reduction of C=C Bonds Fueled by the Biocatalytic Oxidation of Water. Issue 18 (29th March 2016)

• Record Type: Journal Article
• Authors: Köninger, Katharina; Gómez Baraibar, Álvaro; Mügge, Carolin; Paul, Caroline E.; Hollmann, Frank; Nowaczyk, Marc M.; Kourist, Robert
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 18(2016)
• Page Start: 5582
• Page End: 5585
• Publication Date: 2016-03-29
• Subjects: biotechnology -- enzyme catalysis -- photocatalysis -- photosynthesis -- reduction; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201601200
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A recombinant enoate reductase was expressed in cyanobacteria and used for the light‐catalyzed, enantioselective reduction of C=C bonds. The coupling of oxidoreductases to natural photosynthesis allows asymmetric syntheses fueled by the oxidation of water. Bypassing the addition of sacrificial cosubstrates as electron donors significantly improves the atom efficiency and avoids the formation of undesired side products. Crucial factors for product formation are the availability of NADPH and the amount of active enzyme in the cells. The efficiency of the reaction is comparable to typical whole‐cell biotransformations in E. coli. Under optimized conditions, a solution of 100 mg prochiral 2‐methylmaleimide was reduced to optically pure 2‐methylsuccinimide (99 % ee, 80 % yield of isolated product). High product yields and excellent optical purities demonstrate the synthetic usefulness of light‐catalyzed whole‐cell biotransformations using recombinant cyanobacteria. Abstract : Useful bacteria : Recombinant cyanobacteria are able to perform enantioselective redox reactions without the addition of cofactors or sacrificial substrates. This increases the atom efficiency of the process and removes an intrinsic limitation for the use of enzymes in mainstream industrial processes. EWG=electron‐withdrawing group.