Title
Near-infrared light-driven asymmetric photolytic reduction of ketone using inorganic-enzyme hybrid biocatalyst
Author
Qiao, Li (Hangzhou Normal University)
Zhang, Jing (Hangzhou Normal University)
Jiang, Yongjian (Hangzhou Normal University)
Ma, Bianqin (Hangzhou Normal University)
Chen, Haomin (Hangzhou Normal University)
Gao, Peng (Hangzhou Normal University)
Zhang, Pengfei (Hangzhou Normal University)
Wang, Anming (Hangzhou Normal University)
Sheldon, R.A. (TU Delft BT/Biocatalysis; University of Witwatersrand)
Date
2024
Abstract
Effective photolytic regeneration of the NAD(P)H cofactor in enzymatic reductions is an important and elusive goal in biocatalysis. It can, in principle, be achieved using a near-infrared light (NIR) driven artificial photosynthesis system employing H2O as the sacrificial reductant. To this end we utilized TiO2/reduced graphene quantum dots (r-GQDs), combined with a novel rhodium electron mediator, to continuously supply NADPH in situ for aldo-keto reductase (AKR) mediated asymmetric reductions under NIR irradiation. This upconversion system, in which the Ti-O-C bonds formed between r-GQDs and TiO2 enabled efficient interfacial charge transfer, was able to regenerate NADPH efficiently in 64 % yield in 105 min. Based on this, the pharmaceutical intermediate (R)-1-(3,5-bis(trifluoromethyl)phenyl)ethan-1-ol was obtained, in 84 % yield and 99.98 % ee, by reduction of the corresponding ketone. The photo-enzymatic system is recyclable with a polymeric electron mediator, which maintained 66 % of its original catalytic efficiency and excellent enantioselectivity (99.9 % ee) after 6 cycles.
Subject
Aldo-ketone reductase
Cofactor regeneration
Ketone reduction
Photo-enzymatic reduction
TiO/r-GQDs nanocomposite
Upconversion
To reference this document use:
http://resolver.tudelft.nl/uuid:e43792be-e3d8-4f44-a780-a1b1c40370af
DOI
https://doi.org/10.1016/j.ijbiomac.2024.130612
Embargo date
2024-09-04
ISSN
0141-8130
Source
International Journal of Biological Macromolecules, 264
Bibliographical note
Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public.
Part of collection
Institutional Repository
Document type
journal article
Rights
© 2024 Li Qiao, Jing Zhang, Yongjian Jiang, Bianqin Ma, Haomin Chen, Peng Gao, Pengfei Zhang, Anming Wang, R.A. Sheldon