Quaternary Charge-Transfer Complex Enables Photoenzymatic Intermolecular Hydroalkylation of Olefins

Claire G. Page, Simon J. Cooper, Jacob S. Dehovitz, Daniel G. Oblinsky, Kyle F. Biegasiewicz, Alyssa H. Antropow, Kurt W. Armbrust, J. Michael Ellis, Lawrence G. Hamann, Evan J. Horn, Kevin M. Oberg, Gregory D. Scholes, Todd K. Hyster

Research output: Contribution to journalArticlepeer-review

Abstract

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.

Original languageEnglish (US)
Pages (from-to)97-102
Number of pages6
JournalJournal of the American Chemical Society
Volume143
Issue number1
DOIs
StatePublished - Jan 13 2021

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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