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Cobalt-electrocatalytic HAT for functionalization of unsaturated C–C bonds

Author

Listed:
  • Samer Gnaim

    (The Scripps Research Institute (TSRI))

  • Adriano Bauer

    (The Scripps Research Institute (TSRI))

  • Hai-Jun Zhang

    (The Scripps Research Institute (TSRI))

  • Longrui Chen

    (The Scripps Research Institute (TSRI))

  • Cara Gannett

    (Cornell University)

  • Christian A. Malapit

    (University of Utah)

  • David E. Hill

    (The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology)

  • David Vogt

    (University of Utah)

  • Tianhua Tang

    (University of Utah)

  • Ryan A. Daley

    (The Scripps Research Institute (TSRI))

  • Wei Hao

    (The Scripps Research Institute (TSRI))

  • Rui Zeng

    (Cornell University)

  • Mathilde Quertenmont

    (Minakem Recherche)

  • Wesley D. Beck

    (University of Utah)

  • Elya Kandahari

    (The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology)

  • Julien C. Vantourout

    (The Scripps Research Institute (TSRI))

  • Pierre-Georges Echeverria

    (Minakem Recherche)

  • Hector D. Abruna

    (Cornell University)

  • Donna G. Blackmond

    (The Scripps Research Institute (TSRI))

  • Shelley D. Minteer

    (University of Utah)

  • Sarah E. Reisman

    (The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology)

  • Matthew S. Sigman

    (University of Utah)

  • Phil S. Baran

    (The Scripps Research Institute (TSRI))

Abstract

The study and application of transition metal hydrides (TMHs) has been an active area of chemical research since the early 1960s1, for energy storage, through the reduction of protons to generate hydrogen2,3, and for organic synthesis, for the functionalization of unsaturated C–C, C–O and C–N bonds4,5. In the former instance, electrochemical means for driving such reactivity has been common place since the 1950s6 but the use of stoichiometric exogenous organic- and metal-based reductants to harness the power of TMHs in synthetic chemistry remains the norm. In particular, cobalt-based TMHs have found widespread use for the derivatization of olefins and alkynes in complex molecule construction, often by a net hydrogen atom transfer (HAT)7. Here we show how an electrocatalytic approach inspired by decades of energy storage research can be made use of in the context of modern organic synthesis. This strategy not only offers benefits in terms of sustainability and efficiency but also enables enhanced chemoselectivity and distinct, tunable reactivity. Ten different reaction manifolds across dozens of substrates are exemplified, along with detailed mechanistic insights into this scalable electrochemical entry into Co–H generation that takes place through a low-valent intermediate.

Suggested Citation

  • 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.
  • Handle: RePEc:nat:nature:v:605:y:2022:i:7911:d:10.1038_s41586-022-04595-3
    DOI: 10.1038/s41586-022-04595-3
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    Citations

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    Cited by:

    1. Minghui Xue & Zhiqiang Peng & Keyan Tao & Jiong Jia & Datong Song & Chen-Ho Tung & Wenguang Wang, 2024. "Catalytic hydrogenation of olefins by a multifunctional molybdenum-sulfur complex," Nature Communications, Nature, vol. 15(1), pages 1-8, December.
    2. Tanner C. Jankins & Philip M. Blank & Andrea Brugnetti & Philip Boehm & Françoise A. Aouane & Bill Morandi, 2024. "Shuttle HAT for mild alkene transfer hydrofunctionalization," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    3. 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.

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