Quaternary Charge-Transfer Complex Enables Photoenzymatic Intermolecular Hydroalkylation of Olefins
| Autor: | Kyle F. Biegasiewicz, Claire G. Page, Lawrence G. Hamann, Kevin M. Oberg, Gregory D. Scholes, Evan J. Horn, Simon J. Cooper, Daniel G. Oblinsky, Alyssa H. Antropow, Jacob S. Dehovitz, J. Michael Ellis, Todd K. Hyster, Kurt W. Armbrust |
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| Rok vydání: | 2021 |
| Předmět: |
Alkylation
Light Dinitrocresols Chemical Flavin group Alkenes 010402 general chemistry Photochemistry 01 natural sciences Biochemistry Catalysis Article Electron transfer Colloid and Surface Chemistry Models Catalytic Domain Ene reaction chemistry.chemical_classification biology Flavoproteins Chemistry Alkene Intermolecular force Active site General Chemistry Charge-transfer complex Amides 0104 chemical sciences Models Chemical Biocatalysis Chemical Sciences biology.protein Oxidoreductases |
| Zdroj: | Journal of the American Chemical Society, vol 143, iss 1 J Am Chem Soc |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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