Cofactor-Free, Direct Photoactivation of Enoate Reductases for the Asymmetric Reduction of C=C Bonds

Cofactor-Free, Direct Photoactivation of Enoate Reductases for the Asymmetric Reduction of C=C Bonds

Lee, Sahng Ha (Korea Advanced Institute of Science and Technology)
Choi, Da Som (Korea Advanced Institute of Science and Technology)
Pesic, M. (TU Delft BT/Biocatalysis)
Lee, Yang Woo (Korea Advanced Institute of Science and Technology)
Paul, C.E. (TU Delft BT/Biocatalysis)
Hollmann, F. (TU Delft BT/Biocatalysis)
Park, Chan Beum (Korea Advanced Institute of Science and Technology)

2017

Enoate reductases from the family of old yellow enzymes (OYEs) can catalyze stereoselective trans-hydrogenation of activated C=C bonds. Their application is limited by the necessity for a continuous supply of redox equivalents such as nicotinamide cofactors [NAD(P)H]. Visible light-driven activation of OYEs through NAD(P)H-free, direct transfer of photoexcited electrons from xanthene dyes to the prosthetic flavin moiety is reported. Spectroscopic and electrochemical analyses verified spontaneous association of rose bengal and its derivatives with OYEs. Illumination of a white light-emitting-diode triggered photoreduction of OYEs by xanthene dyes, which facilitated the enantioselective reduction of C=C bonds in the absence of NADH. The photoenzymatic conversion of 2-methylcyclohexenone resulted in enantiopure (ee>99 %) (R)-2-methylcyclohexanone with conversion yields as high as 80–90 %. The turnover frequency was significantly affected by the substitution of halogen atoms in xanthene dyes.

asymmetric reduction
enoate reductases
green chemistry
photocatalysis
redox enzymes

http://resolver.tudelft.nl/uuid:88f58b61-ca5e-47ed-9cc9-b848e115e54c

https://doi.org/10.1002/anie.201702461

1433-7851

Angewandte Chemie (International Edition), 56 (30), 8681-8685

Institutional Repository

journal article

© 2017 Sahng Ha Lee, Da Som Choi, M. Pesic, Yang Woo Lee, C.E. Paul, F. Hollmann, Chan Beum Park