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Bioinspired desaturation of alcohols enabled by photoredox proton-coupled electron transfer and cobalt dual catalysis

Author

Listed:
  • Long Huang

    (RWTH Aachen University)

  • Tengfei Ji

    (RWTH Aachen University)

  • Chen Zhu

    (King Abdullah University of Science and Technology (KAUST))

  • Huifeng Yue

    (King Abdullah University of Science and Technology (KAUST))

  • Nursaya Zhumabay

    (King Abdullah University of Science and Technology (KAUST))

  • Magnus Rueping

    (King Abdullah University of Science and Technology (KAUST))

Abstract

In the biosynthesis sterols an enzyme-catalyzed demethylation is achieved via a stepwise oxidative transformation of alcohols to olefins. The overall demethylation proceeds through two sequential monooxygenation reactions and a subsequent dehydroformylative saturation. To mimic the desaturation processes observed in nature, we have successfully integrated photoredox proton-coupled electron transfer (PCET) and cobaloxime chemistry for the acceptorless dehydrogenation of alcohols. The state-of-the-art remote and precise desaturation of ketones proceeds efficiently through the activation of cyclic alcohols using bond-dissociation free energy (BDFE) as thermodynamic driving force. The resulting transient alkoxyl radical allows C-C bond scission to generate the carbon-centered radical remote to the carbonyl moiety. This key intermediate is subsequently combined with cobaloxime photochemistry to furnish the alkene. Moreover, the mild protocol can be extended to desaturation of linear alcohols as well as aromatic hydrocarbons. Application to bioactive molecules and natural product derivatives is also presented.

Suggested Citation

  • Long Huang & Tengfei Ji & Chen Zhu & Huifeng Yue & Nursaya Zhumabay & Magnus Rueping, 2022. "Bioinspired desaturation of alcohols enabled by photoredox proton-coupled electron transfer and cobalt dual catalysis," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-28441-2
    DOI: 10.1038/s41467-022-28441-2
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    References listed on IDEAS

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    1. Julian G. West & David Huang & Erik J. Sorensen, 2015. "Acceptorless dehydrogenation of small molecules through cooperative base metal catalysis," Nature Communications, Nature, vol. 6(1), pages 1-7, December.
    2. Shashikant Dighe & Fabio Juliá & Alberto Luridiana & James J. Douglas & Daniele Leonori, 2020. "A photochemical dehydrogenative strategy for aniline synthesis," Nature, Nature, vol. 584(7819), pages 75-81, August.
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    Cited by:

    1. Yuanli Xu & Wenlong Chen & Ruihua Pu & Jia Ding & Qing An & Yi Yang & Weimin Liu & Zhiwei Zuo, 2024. "Selective monodeuteration enabled by bisphosphonium catalyzed ring opening processes," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    2. Chen Zhu & Huifeng Yue & Magnus Rueping, 2022. "Nickel catalyzed multicomponent stereodivergent synthesis of olefins enabled by electrochemistry, photocatalysis and photo-electrochemistry," Nature Communications, Nature, vol. 13(1), pages 1-9, December.

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