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PreprintCC BY-NC-NDChemRxiv

Zr-MOF/Quinone Multicatalysis Enables Programmable Aerobic Synthesis of Benzimidazoles

  • Juan Camilo Arango-Daza1,2,3,4
  • Spandan Hati1,2,3,4
  • Sakarn Khamkaeo5,6
  • Yuttapoom Puttisong5,6
  • Miguel A. Rivero-Crespo1,2,3,4
6 affiliations
  1. 1Wallenberg Initiative Materials Science for Sustainability
  2. 2Department of Chemistry, Stockholm University
  3. 3Department of Chemistry
  4. 4Stockholm University
  5. 5Department of Physics, Chemistry, and Biology (IFM
  6. 6Linköping University
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Abstract

Selectivity control in aerobic oxidation reactions containing several oxidizable functional groups remains challenging. Herein, we show that the chemoselectivity of a Zr-MOF/quinone 2 multicatalytic platform can be controlled through modulation of the organic redox co-catalyst. In contrast to previously reported Zr-MOF-808/(hydro)quinone combinations that promote direct oxidation of anilines or thiols, Zr-MOF-808/1,8-dichloroanthraquinone unlocks a different reaction pathway to selectively oxidize primary alcohols in the presence of aromatic diamines and aminothiophenols. This pathway enables the one-pot synthesis of 2-substituted benzimidazoles and benzothiazoles under atmospheric air. Mechanistic experiments support coupled catalytic cycles in which Lewis-acidic Zr sites facilitate quinone-mediated alcohol oxidation, while the MOF/semiquinone interface regenerates the oxidized mediator using oxygen. This method furnishes a highly sustainable synthesis of 31 benzimidazole and benzothiazole products, permitting recovery and reuse of both catalytic components.

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Cite

BibTeXRIS
BibTeX
@misc{arangodaza2026zrmofquinone,
  title = {{Zr-MOF/Quinone Multicatalysis Enables Programmable Aerobic Synthesis of Benzimidazoles}},
  author = {Juan Camilo Arango-Daza and Spandan Hati and Sakarn Khamkaeo and Yuttapoom Puttisong and Miguel A. Rivero-Crespo},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010252/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010252/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - Zr-MOF/Quinone Multicatalysis Enables Programmable Aerobic Synthesis of Benzimidazoles
AU  - Juan Camilo Arango-Daza
AU  - Spandan Hati
AU  - Sakarn Khamkaeo
AU  - Yuttapoom Puttisong
AU  - Miguel A. Rivero-Crespo
PY  - 2026
DA  - 2026/10/12
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010252/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010252/v1
AB  - Selectivity control in aerobic oxidation reactions containing several oxidizable functional groups remains challenging. Herein, we show that the chemoselectivity of a Zr-MOF/quinone 2 multicatalytic platform can be controlled through modulation of the organic redox co-catalyst. In contrast to previously reported Zr-MOF-808/(hydro)quinone combinations that promote direct oxidation of anilines or thiols, Zr-MOF-808/1,8-dichloroanthraquinone unlocks a different reaction pathway to selectively oxidize primary alcohols in the presence of aromatic diamines and aminothiophenols. This pathway enables the one-pot synthesis of 2-substituted benzimidazoles and benzothiazoles under atmospheric air. Mechanistic experiments support coupled catalytic cycles in which Lewis-acidic Zr sites facilitate quinone-mediated alcohol oxidation, while the MOF/semiquinone interface regenerates the oxidized mediator using oxygen. This method furnishes a highly sustainable synthesis of 31 benzimidazole and benzothiazole products, permitting recovery and reuse of both catalytic components.
ER  -