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Mechanism of copper-free Sonogashira reaction operates through palladium-palladium transmetallation

Author

Listed:
  • Martin Gazvoda

    (University of Ljubljana)

  • Miha Virant

    (University of Ljubljana)

  • Balazs Pinter

    (Universidad Técnico Federico Santa María
    Vrije Universiteit Brussel)

  • Janez Košmrlj

    (University of Ljubljana)

Abstract

The seminal contributions by Sonogashira, Cassar and Heck in mid 1970s on Pd/Cu- and Pd-catalysed (copper-free) coupling of acetylenes with aryl or vinyl halides have evolved in myriad applications. Despite the enormous success both in academia and in industry, however, critical mechanistic questions of this cross-coupling process remain unresolved. In this study, experimental evidence and computational support is provided for the mechanism of copper-free Sonogashira cross-coupling reaction. In contrast to the consensus monometallic mechanism, the revealed pathway proceeds through a tandem Pd/Pd cycle linked via a multistep transmetallation process. This cycle is virtually identical to the Pd/Cu tandem mechanism of copper co-catalysed Sonogashira cross-couplings, but the role of CuI is played by a set of PdII species. Phosphine dissociation from the square-planar reactants to form transient three-coordinate Pd species initiates transmetallation and represents the rate-determining step of the process.

Suggested Citation

  • Martin Gazvoda & Miha Virant & Balazs Pinter & Janez Košmrlj, 2018. "Mechanism of copper-free Sonogashira reaction operates through palladium-palladium transmetallation," Nature Communications, Nature, vol. 9(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:9:y:2018:i:1:d:10.1038_s41467-018-07081-5
    DOI: 10.1038/s41467-018-07081-5
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    Cited by:

    1. Che Lah, Nurul Akmal, 2021. "Late transition metal nanocomplexes: Applications for renewable energy conversion and storage," Renewable and Sustainable Energy Reviews, Elsevier, vol. 145(C).

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