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Paired electrocatalysis unlocks cross-dehydrogenative coupling of C(sp3)-H bonds using a pentacoordinated cobalt-salen catalyst

Author

Listed:
  • Ke Liu

    (Anhui University)

  • Mengna Lei

    (Anhui University)

  • Xin Li

    (Anhui University)

  • Xuemei Zhang

    (Anhui University)

  • Ying Zhang

    (Anhui University)

  • Weigang Fan

    (Anhui University)

  • Man-Bo Li

    (Anhui University)

  • Sheng Zhang

    (Anhui University)

Abstract

Cross-dehydrogenative coupling of C(sp3)-H bonds is an ideal approach for C(sp3)-C(sp3) bond construction. However, conventional approaches mainly rely on a single activation mode by either stoichiometric oxidants or electrochemical oxidation, which would lead to inferior selectivity in the reaction between similar C(sp3)-H bonds. Herein we describe our development of a paired electrocatalysis strategy to access an unconventional selectivity in the cross-dehydrogenative coupling of alcoholic α C(sp3)-H with allylic (or benzylic) C-H bonds, which combines hydrogen evolution reaction catalysis with hydride transfer catalysis. To maximize the synergistic effect of the catalyst combinations, a HER catalyst pentacoordinated Co-salen is disclosed. The catalyst displays a large redox-potential gap (1.98 V) and suitable redox potential. With the optimized catalyst combination, an electrochemical cross-dehydrogenative coupling protocol features unconventional chemoselectivity (C-C vs. C-O coupling), excellent functional group tolerance (84 examples), valuable byproduct (hydrogen), and high regio- and site-selectivity. A plausible reaction mechanism is also proposed to rationalize the experimental observations.

Suggested Citation

  • Ke Liu & Mengna Lei & Xin Li & Xuemei Zhang & Ying Zhang & Weigang Fan & Man-Bo Li & Sheng Zhang, 2024. "Paired electrocatalysis unlocks cross-dehydrogenative coupling of C(sp3)-H bonds using a pentacoordinated cobalt-salen catalyst," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-47220-9
    DOI: 10.1038/s41467-024-47220-9
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    References listed on IDEAS

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    1. Ganceng Yang & Yanqing Jiao & Haijing Yan & Ying Xie & Chungui Tian & Aiping Wu & Yu Wang & Honggang Fu, 2022. "Unraveling the mechanism for paired electrocatalysis of organics with water as a feedstock," Nature Communications, Nature, vol. 13(1), pages 1-12, December.
    2. Samer Gnaim & Adriano Bauer & Hai-Jun Zhang & Longrui Chen & Cara Gannett & Christian A. Malapit & David E. Hill & David Vogt & Tianhua Tang & Ryan A. Daley & Wei Hao & Rui Zeng & Mathilde Quertenmont, 2022. "Cobalt-electrocatalytic HAT for functionalization of unsaturated C–C bonds," Nature, Nature, vol. 605(7911), pages 687-695, May.
    3. Artavazd Badalyan & Shannon S. Stahl, 2016. "Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators," Nature, Nature, vol. 535(7612), pages 406-410, July.
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