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Peer-reviewedCC BYJournal of the American Chemical Society

Regenerable Heterogeneous Palladium Single-Atom Catalysts for Direct C-H Arylation.

  • Valentas Olikauskas1,2
  • Marc-Eduard Usteri3,2
  • Aram Bugaev4,2
  • Milivoj Plodinec5,6
  • Sharon Mitchell3,2
  • Jerome Waser1,2
  • Javier Pérez-Ramírez3,2
6 affiliations
  1. 1Laboratory of Catalysis and Organic Synthesis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, Avenue F. A. Forel 2, Lausanne1015, Switzerland.
  2. 2NCCR Catalysis, Zürich8093, Switzerland.
  3. 3Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, Zürich8093, Switzerland.
  4. 4Scherrer Institute , Forschungsstrasse 111, Villigen5232, Switzerland.
  5. 5Scientific Center for Optical and Electron Microscopy, ETH Zürich, Otto-Stern-Weg 3, Zürich8093, Switzerland.
  6. 6Laboratory of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 2, Zürich8093, Switzerland.
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Abstract

Single-atom catalysts (SACs) offer tunable, recoverable heterogeneous alternatives to homogeneous metal complexes in handle-based cross-coupling reactions. However, their application to direct C-H bond functionalization remains unexplored beyond photochemical methods, as the elevated temperature and demanding reaction conditions place stringent requirements on catalyst stability. Here, we demonstrate a Pd single-atom-catalyzed C-H arylation of indoles, extending heterogeneous SACs to thermal C-H functionalization and achieving cumulative turnover numbers above 200 across five cycles. Among diverse oxygen- and nitrogen-coordinated SACs, nitrogen-coordinated sites in Pd@C3N4 uniquely combined metal retention with high activity after phosphine activation. Recycling studies coupled with in situ X-ray absorption spectroscopy reveal Pd-I bond formation as the dominant catalyst deactivation pathway. Guided by this insight, postreaction treatment in aqueous ammonia overcomes iodide poisoning, enabling catalytic activity over multiple cycles. These findings establish design principles for balancing activity, stability, and regenerability in Pd SACs for demanding C-H functionalizations, advancing their potential for greener, more step-efficient chemical synthesis.

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Cite

BibTeXRIS
BibTeX
@article{olikauskas2026regenerable,
  title = {{Regenerable Heterogeneous Palladium Single-Atom Catalysts for Direct C-H Arylation.}},
  author = {Valentas Olikauskas and Marc-Eduard Usteri and Aram Bugaev and Milivoj Plodinec and Sharon Mitchell and Jerome Waser and Javier Pérez-Ramírez},
  journal = {Journal of the American Chemical Society},
  year = {2026},
  month = oct,
  doi = {10.1021/jacs.6c11697},
  url = {https://europepmc.org/article/MED/42954571},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Regenerable Heterogeneous Palladium Single-Atom Catalysts for Direct C-H Arylation.
AU  - Valentas Olikauskas
AU  - Marc-Eduard Usteri
AU  - Aram Bugaev
AU  - Milivoj Plodinec
AU  - Sharon Mitchell
AU  - Jerome Waser
AU  - Javier Pérez-Ramírez
PY  - 2026
DA  - 2026/10/01
JO  - Journal of the American Chemical Society
DO  - 10.1021/jacs.6c11697
UR  - https://europepmc.org/article/MED/42954571
AB  - Single-atom catalysts (SACs) offer tunable, recoverable heterogeneous alternatives to homogeneous metal complexes in handle-based cross-coupling reactions. However, their application to direct C-H bond functionalization remains unexplored beyond photochemical methods, as the elevated temperature and demanding reaction conditions place stringent requirements on catalyst stability. Here, we demonstrate a Pd single-atom-catalyzed C-H arylation of indoles, extending heterogeneous SACs to thermal C-H functionalization and achieving cumulative turnover numbers above 200 across five cycles. Among diverse oxygen- and nitrogen-coordinated SACs, nitrogen-coordinated sites in Pd@C3N4 uniquely combined metal retention with high activity after phosphine activation. Recycling studies coupled with in situ X-ray absorption spectroscopy reveal Pd-I bond formation as the dominant catalyst deactivation pathway. Guided by this insight, postreaction treatment in aqueous ammonia overcomes iodide poisoning, enabling catalytic activity over multiple cycles. These findings establish design principles for balancing activity, stability, and regenerability in Pd SACs for demanding C-H functionalizations, advancing their potential for greener, more step-efficient chemical synthesis.
SN  - 0002-7863
SN  - 1520-5126
ER  -