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Quaternary Charge-Transfer Complex Enables Photoenzymatic In-termolecular Hydroalkylation of Olefins

preprint
submitted on 01.11.2020, 00:51 and posted on 02.11.2020, 12:17 by Claire Page, Simon Cooper, Jacob DeHovitz, Daniel G. Oblinsky, Kyle Biegasiewicz, Alyssa Antropow, Kurt Armbrust, Michael Ellis, Lawrence G. Hamann, Evan Horn, Kevin Oberg, Gregory Scholes, Todd Hyster
Intermolecular C–C bond-forming reactions are underdeveloped transformations in the field of biocatalysis. Here we report a photoenzymatic intermolecular hydroalkylation of olefins catalyzed by flavin-dependent ‘ene’reductases. Radical initiation occurs via photoexcitation of a rare high-order enzyme-templated charge-transfer complex that forms between an alkene, 𝛼-chloroamide, and flavin hydroquinone. This unique mechanism ensures that radical formation only occurs when both substrates are present within the protein active site. This active site can control the radical terminating hydrogen atom transfer, enabling the synthesis of enantioenriched γ-stereogenic amides. This work highlights the potential for photoenzymatic catalysis to enable new biocatalytic transformations via previously unknown electron transfer mechanisms.

Funding

NIGMS R01 GM127703

Bioinspired Light-Escalated Chemistry (BioLEC)

Basic Energy Sciences

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History

Email Address of Submitting Author

thyster@Princeton.edu

Institution

Princeton University

Country

USA

ORCID For Submitting Author

0000-0003-3560-355X

Declaration of Conflict of Interest

There is no conflict of interest.

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