Photoenzymatic Reductions Enabled by Direct Excitation of Flavin-Dependent “Ene”-Reductases

Non-natural photoenzymatic reactions reported to date have depended on the excitation of electron donor–acceptor complexes formed between substrates and cofactors within protein active sites to facilitate electron transfer. While this mechanism has unlocked new reactivity, it limits the types of sub...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2020-12, Vol.143 (4)
Main Authors: Sandoval, Braddock A., Clayman, Phillip D., Oblinsky, Daniel G., Oh, Seokjoon, Nakano, Yuji, Bird, Matthew, Scholes, Gregory D., Hyster, Todd K.
Format: Article
Language:English
Subjects:
Amides
Charge transfer
Flavins
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Peptides and proteins
Transfer reactions
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Summary:Non-natural photoenzymatic reactions reported to date have depended on the excitation of electron donor–acceptor complexes formed between substrates and cofactors within protein active sites to facilitate electron transfer. While this mechanism has unlocked new reactivity, it limits the types of substrates that can be involved in this area of catalysis. Here we demonstrate that direct excitation of flavin hydroquinone within “ene”-reductase active sites enables new substrates to participate in photoenzymatic reactions. We found that by using photoexcitation these enzymes gain the ability to reduce acrylamides through a single electron transfer mechanism.
ISSN:0002-7863
1520-5126