E. coli Nickel-Iron Hydrogenase 1 Catalyses Non-native Reduction of Flavins: Demonstration for Alkene Hydrogenation by Old Yellow Enzyme Ene-reductases*.

Shiny Joseph Srinivasan,Holly A. Reeve,Kylie A. Vincent,Caroline E. Paul,Sarah E. Cleary,Miguel A. Ramirez

doi:10.1002/anie.202101186

Shiny Joseph Srinivasan, Holly A. Reeve + Show 4 more

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https://doi.org/10.1002/anie.202101186

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Abstract

A new activity for the [NiFe] uptake hydrogenase 1 of Escherichia coli (Hyd1) is presented. Direct reduction of biological flavin cofactors FMN and FAD is achieved using H2 as a simple, completely atom‐economical reductant. The robust nature of Hyd1 is exploited for flavin reduction across a broad range of temperatures (25–70 °C) and extended reaction times. The utility of this system as a simple, easy to implement FMNH2 or FADH2 regenerating system is then demonstrated by supplying reduced flavin to Old Yellow Enzyme “ene‐reductases” to support asymmetric alkene reductions with up to 100 % conversion. Hyd1 turnover frequencies up to 20.4 min−1 and total turnover numbers up to 20 200 were recorded during flavin recycling.

Highlights

A new activity for the [NiFe] uptake hydrogenase 1 of Escherichia coli (Hyd1) is presented
The fact that electron transfer from hydrogenases to electrodes is wellestablished[21,25] encouraged us to explore scope for other nonnatural electron transfer reactions of robust Hyd1 from E. coli. We demonstrate that both FMN and FAD can accept electrons from H2 oxidation by Hyd1 to generate FMNH2 and FADH2 respectively, and show that Hyd1 can be used as an effective FMNH2 regeneration system to support asymmetric alkene reduction by three Old Yellow Enzyme (OYE)-type ene-reductases
Conversion of FMN and FAD to the reduced forms after 30 min reaction time increased with temperature (Figure 3), suggesting that Hyd1 is likely to open new doors to cofactor recycling for flavoenzymes with optimal activity at higher temperatures

Summary

Delft University of Technology

E. coli Nickel-Iron Hydrogenase 1 Catalyses Non-native Reduction of Flavins Demonstration for Alkene Hydrogenation by Old Yellow Enzyme Ene-reductases**. Joseph Srinivasan, Shiny; Cleary, Sarah E.; Ramirez, Miguel A.; Reeve, Holly A.; Paul, Caroline E.; Vincent, Kylie A. Publication date 2021 Document Version Final published version Published in Angewandte Chemie - International Edition. Citation (APA) Joseph Srinivasan, S., Cleary, S. Important note To cite this publication, please use the final published version (if applicable).

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